EP1440974A2 - Alkylenedioxythiophenes and Poly(alkylendioxythiophenes) with mesogenic groups - Google Patents

Abstract

3,4-Alkylene dioxythiophenes substituted with a mesogenic group (optionally via a linking group) are new, not including 3,4-ethylenedioxy-thiophene substituted in the ethylenedioxy bridge with a 4'-cyano-biphenyloxy-hexyloxymethyl group. Independent claims are also included for (1) polythiophenes with repeating units of formula (IV), not including those with units of formula (ii); (2) methods for the production of polythiophenes by the electrochemical or chemical oxidative polymerization of the corresponding thiophene compounds (I); and (3) polythiophenes obtained by this method. A = 1-5C alkylene, optionally with a linker L at any point and optionally with other substituents; L = methylene; p = 0 or 1-6; M = an n-functional mesogenic group; n = 1-8; B1 = linking group of formula -(CO)q-(Sp)m-(CO)r-(Q)t-(CO)s-; q, t, m = 0 or 1; r, s = 0 or 1, with the proviso that s is 0 when r is 1 and vice versa, or both are zero; Sp = a spacer selected from optionally substituted linear or cyclic 1-20C alkylene, 5-20C arylene, 2-20C heteroarylene (optionally with 1-3 other N, O or S atoms in the heteroaromatic ring), 6-20C aralkylene, or a 2-200C oligo- or poly-ether group; and Q = O, S or NH.

Description

The invention relates to new 3,4-alkylenedioxythiophenes substituted with mesogenic Groups and their polymeric derivatives (poly (3,4-alkylenedioxythiophenes)).

π-conjugated polymers show because of the considerable delocalization of the π electrons interesting (non-linear) optical properties along the main chain. After oxidation or reduction, they are good electrical conductors and in the neutral form they also have good semiconducting properties. Therefore they are for use in areas such as data storage, optical Signal processing, electromagnetic interference suppression (EMI) and of solar energy conversion, as well as in rechargeable batteries, light emitting Diodes, field effect transistors, circuit boards, sensors and antistatic Materials of interest.

Poly (3,4-alkylenedioxythiophenes) and their derivatives, in particular poly (3,4-ethylenedioxythiophene) and their derivatives, are of particular interest owing to their high conductivities, especially in the cationic (oxidized) form and good processability (EP-A 339 340 and L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik & JR Reynolds, Adv. Mater. 12 , (2000) pp. 481-494).

Despite the good properties of poly (3,4-ethylenedioxythiophene) s in terms of conductivity and processability, there is a need for further improvements. For the Application, for example in molecular electronics, solar or semiconductor technology are high demands on the conductive or semiconducting Materials provided. Order phenomena play a particularly important role.

Because the processing of conductive or semiconducting polymers predominantly consists of liquid phase, e.g. Solution, suspension or dispersion, can take place on a Preorientation to high order in the solid phase has so far had no influence become. However, it would be conceivable to have such pre-orientation through self-organization to achieve the monomers in the polymerization by structural Prerequisites for short-range orders are created.

Several attempts have already been described in the literature, π-conjugated polymers to produce the mesogenic groups, i.e. Groups that are mesogenic Favor phases, wear as substituents.

Attempts to prepare thiophenes with mesogenic substituents or their polymeric secondary products have also been described in some publications. For example, J. Roncali et al. (Adv. Mater. 1994 , 6 (2), pp. 138-142) the synthesis of 4-cyan-4 '- (8- (3-thienyl) oxy) biphenyl, its liquid crystalline behavior and the electrochemical polymerization to give the corresponding polythiophene , Its electrical conductivity is specified as 0.01 to 0.1 S / cm. Akagi et al. report in Synthetic Metals 1999 , 102, p. 1291, about liquid-crystalline polythiophenes with chiral mesogenic groups as substituents without further information on electrical properties. Kijima et al. reports on a cationic, viologen-substituted liquid-crystalline polythiophene, describes its redox behavior and the electrical conductivity of 3.5 x 10 ^-3 S / cm in the J ₂ -doped state, which, however, is extremely low with regard to the above-mentioned applications (Chem. Letters 2000 , pp. 936-937). Yagci et al. describes the preparation of the liquid-crystalline 3-thiopheneacetic acid cholesteryl ester, which was polymerized chemically and electrochemically oxidatively to polythiophene with a conductivity of 0.05 S / cm (J. Mater. Sci. 2002 , 37, pp. 1767 - 1775).

For all polythiophenes described in the cited literature references, two structurally determined disadvantages are characteristic. First, the substitution only in position 3 of the thiophene unit leads to side reactions in the polymerization, since a reactive H is located as the substituent in the 4-position; The so-called α, β'-coupling in particular can lead to structural defects, that is to say the interruption of the conjugation in the polymer and shortened conjugation lengths with the consequence of inadequate conductivities. Secondly, the thiophenes substituted in the C position only in the 3-position always lead to only moderate stability of the highly conductive cationic state of the polythiophenes (e.g. after iodine doping). Such adverse effects are well known for analog, non-liquid crystalline polythiophenes, see e.g. B. Leclerc et al., Macromolecules 1991, 24, pp. 455-459.

Kumar et al. described in Synthetic Metals 2001, 124, pp. 471 - 475 a 3,4-ethylenedioxythiophene with bulky substituents as well as its electrochemical polymerization to the correspondingly substituted poly (3,4-ethylenedioxythiophene) as well as studies of these polymers under the aspect of improved transparency. Although the bulky substituent can be viewed as a potential mesogenic group, no evidence of liquid crystalline behavior of the monomer or polymer or investigations have been given.

There was therefore still a need for 3,4-alkylenedioxythiophenes, the mesogenic Wear groups as substituents.

The present invention thus relates to 3,4-alkylenedioxythiophenes, characterized in that they are optionally substituted by a link B with a mesogenic group M,
except the 3,4-alkylenedioxythiophene of the formula (i)

The term mesogenic group is known to the person skilled in the art. Everyone will be among them Understood groups or substances that are suitable in a particular Temperature range to form mesophases, i.e. Phases with a higher order status than in isotropic liquids, but with a lower one than in crystals. Such phases (still) show the optical anisotropy of crystals and (already) that Mobility of consistently isotropic liquids. Mesophases are also called called liquid crystalline phases or anisotropic liquids.

Within the scope of the invention, the mesogenic group can be one which is used for Formation of smectic, nematic or cholesteric liquid-crystalline phases is suitable is. This can be rod-shaped, disc-shaped (discotic) or cholesteric mesogenic groups.

worin

A

für einen C₁-C₅-Alkylenrest steht, der an beliebiger Stelle durch einen Linker L substituiert ist und gegebenenfalls weitere Substituenten trägt,

L

für eine Methylengruppe steht,

p

für 0 oder eine ganze Zahl von 1 bis 6, bevorzugt für 0 oder 1 steht,

M

für eine n-funktionelle mesogene Gruppe steht,

n

für eine ganze Zahl von 1 bis 8 steht und

B

für ein Bindeglied der allgemeinen Formel (B) steht

worin

q

für 0 oder 1 steht,

r, s

für 0 oder 1 stehen, mit der Maßgabe, dass wenn r für 1 steht s für 0 steht und umgekehrt oder beide für 0 stehen können,

t

für 0 oder 1 steht,

Sp

für einen Spacer ausgewählt aus gegebenenfalls substituierten linearen oder cylischen C₁-C₂₀-Alkylen-, C₅-C₂₀-Arylen-, C₂-C₂₀-Heteroarylen-, wobei zusätzlich noch ein bis drei Heteroatome ausgewählt aus N, O oder S im heteroaromatischen Ring- oder Ringsystem vorhanden sein können, C₆-C₂₀-Aralkylen-, C₂-C₂₀₀-, bevorzugt C₂-C₈₀-Oligo- oder -Polyethergruppen steht,

m

für 0 oder 1 steht,

Q

für O, S oder NH steht.

The present invention preferably relates to 3,4-alkylenedioxythiophenes of the general formula (I)

wherein

A

represents a C ₁ -C ₅ alkylene radical which is substituted at any point by a linker L and optionally carries further substituents,

L

represents a methylene group,

p

represents 0 or an integer from 1 to 6, preferably 0 or 1,

M

represents an n-functional mesogenic group,

n

represents an integer from 1 to 8 and

B

represents a link of the general formula (B)

wherein

q

represents 0 or 1,

r, s

stand for 0 or 1, with the proviso that if r stands for 1 s stands for 0 and vice versa or both can stand for 0,

t

represents 0 or 1,

sp

for a spacer selected from optionally substituted linear or cyclic C ₁ -C ₂₀ alkylene, C ₅ -C ₂₀ arylene, C ₂ -C ₂₀ heteroarylene, with additionally one to three heteroatoms selected from N, O or S can be present in the heteroaromatic ring or ring system, C ₆ -C ₂₀ aralkylene, C ₂ -C ₂₀₀ , preferably C ₂ -C ₈₀ oligo- or polyether groups,

m

represents 0 or 1,

Q

represents O, S or NH.

Both pure 3,4-alkylenedioxythiophenes of the general formula (I) are as any mixtures of these also encompassed by the invention.

worinThese are particularly preferably 3,4-alkylenedioxythiophenes or mixtures of 3,4-alkylenedioxythiophenes which have a structure of the general formula (Ia) and / or (Ib),

wherein

B and M are the same for the general formula (I) and / or the following Have meaning.

If it is a mixture of 3,4-alkylenedioxythiophenes of the general Formula (I-a) and (I-b) can be used in the context of the invention 3,4-alkylenedioxythiophenes of the general formulas (I-a) and (I-b) in any molar ratio be contained in this mixture. 3,4-Alkylenedioxythiophenes are preferred of the general formula (I-a) with a proportion of 65 to 99.9%, particularly preferably in a proportion of 75 to 99.5%, based on the total amount of substance of thiophenes, and the 3,4-alkylenedioxythiophenes of the general Formula (I-b) are preferred in a proportion of 0.1 to 35%, particularly preferred with a share of 0.5 to 25%, based on the total amount of Thiophene contain, with the proviso that the sum of both parts is 100%.

Preferably, within the scope of the invention

M

für eine n-funktionelle Gruppe der allgemeinen Formeln (II-a) oder (II-b) stehen,

worin

X¹, X², X³

unabhängig voneinander für gegebenenfalls substituierte Strukturen ausgewählt aus

Z¹, Z² unabhängig voneinander für Strukturen ausgewählt aus

steht,
wobei

R^x und R^y

unabhängig voneinander für H, gegebenenfalls substituiertes C₁-C₂₂-Alkyl, C₁-C₂₂-Halogenalkyl, C₁-C₂₂-Alkenyl, C₁-C₂₂-Alkoxy, C₁-C₂₂-Thioalkyl, C₁-C₂₂-Iminoalkyl, C₁-C₂₂-Alkoxycarbonyl, C₁- C₂₂-Alkoxycarbonyloxy, einen Rest einer aliphatischen C₁-C₂₂-Alkancarbonsäure oder der Acrylsäure, Halogen, Pseudohalogen, NO₂, eine Carboxyl- oder eine Hydroxygruppe steht,

h

für eine ganze Zahl von 1 bis 10 steht,

w

eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 3, ist,

x, y, z

unabhängig voneinander für 0 oder 1 stehen, und

n

für 1 oder 2 steht, wobei
für den Fall, dass n für 1 steht, die Gruppe der allgemeinen Formeln (II-a) oder (II-b) an einer der mit * gekennzeichneten Verknüpfungsstellen eine Flügelgruppe F trägt,
wobei

F

für H, gegebenenfalls substituiertes C₁-C₂₂-Alkyl, C₁-C₂₂-Halogenalkyl, C₁-C_22-Alkenyl, C_1-C₂₂-Alkoxy, C_1-C_22-Thioalkyl, C_1-C₂₂-Iminoalkyl, C₁-C₂₂-Alkoxycarbonyl, C₁-C₂₂-Alkoxycarbonyloxy, einen Rest einer aliphatischen C₁-C₂₂-Alkancarbonsäure oder der Acrylsäure, Halogen, Pseudohalogen, eine Nitro- (NO₂-), eine Carboxyl-, eine Sulfonsäure- bzw. Sulfonat- oder eine Hydroxygruppe steht.

M

represent an n-functional group of the general formulas (II-a) or (II-b),

wherein

X ¹ , X ² , X ³

independently selected for optionally substituted structures

Z ¹ , Z ² are selected independently of one another for structures

stands,
in which

R ^x and R ^y

independently of one another for H, optionally substituted C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ - C _{22-iminoalkyl,} C ₁ -C ₂₂ alkoxycarbonyl, C ₁ - C ₂₂ alkoxycarbonyloxy, a radical of an aliphatic C ₁ -C ₂₂ alkanecarboxylic acid or acrylic acid, halogen, pseudo-halogen, NO _2, a carboxyl or a hydroxyl group is .

H

represents an integer from 1 to 10,

w

is an integer from 1 to 5, preferably 1 to 3,

x, y, z

independently represent 0 or 1, and

n

represents 1 or 2, where
in the event that n stands for 1, the group of the general formulas (II-a) or (II-b) bears a wing group F at one of the linking points marked with *,
in which

F

is H, optionally substituted C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C _1- C ₂₂ alkoxy, C _1- C _22- thioalkyl, C _1- C ₂₂ Iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, pseudohalogen, a nitro (NO ₂ -), a carboxyl , a sulfonic acid or sulfonate or a hydroxy group.

In preferred embodiments of the invention, in which M represents an n-functional group of the general formula (II-a), w represents an integer from 2 to 5, where X ¹ , n and F can have the meaning given above.

A peculiarity occurs when w stands for 1 in the general formula (II-a). In this case, X ¹ at one of the linking points marked with * as wing group F, for example a carboxyl group -COOH or an acrylic acid residue, e.g. B. -CH = CH-COOH, so that a mesogenic group is formed by dimerization.

Therefore, in other preferred embodiments of the invention, where M is an n-functional group of the general formula (II-a), w is 1, n is 1 and F is a carboxyl group -COOH or an acrylic acid residue -CH = CH-COOH , in particular when X ^{1 stands} for monocyclic structures from the selection mentioned above for X ¹ .

Optional substituents for X ¹ , X ² and X ³ include, for example, linear, branched or cyclic C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy , C ₁ -C ₂₂ thioalkyl, C ₁ -C ₂₂ iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, Pseudohalogen, NO _{2 is} a carboxyl or a hydroxy group.

In preferred embodiments of the present invention, X ¹ , X ² and X ^{3 are} unsubstituted.

Can also be preferred within the scope of the invention

M

für eine n-funktionelle Gruppe ausgewählt aus den allgemeinen Formeln (II-c-1) bis (II-c-6) stehen,

worin

n

für eine ganze Zahl von 1 bis 8 steht, wobei

für den Fall, dass n für eine ganze Zahl kleiner als 8 steht, die Gruppe ausgewählt aus den allgemeinen Formeln (II-c-1) bis (II-c-6) an den restlichen 8 - n mit * gekennzeichneten Verknüpfungsstellen eine Flügelgruppe F trägt,
wobei

F

für H, gegebenenfalls substituiertes C₁C₂₂-Alkyl, C₁-C₂₂-Halogenalkyl, C₁-C₂₂-Alkenyl, C₁-C₂₂-Alkoxy, C₁-C₂₂-Thioalkyl, C₁-C₂₂-Iminoalkyl, C₁-C₂₂-Alkoxycarbonyl, C₁-C₂₂-Alkoxycarbonyloxy, einen Rest einer aliphatischen C₁-C₂₂-Alkancarbonsäure oder der Acrylsäure, Halogen, Pseudohalogen, NO₂, eine Carboxyl-, eine Sulfonsäure- bzw. Sulfonat- oder eine Hydroxygruppe steht.

M

stand for an n-functional group selected from the general formulas (II-c-1) to (II-c-6),

wherein

n

represents an integer from 1 to 8, where

in the event that n stands for an integer less than 8, the group selected from the general formulas (II-c-1) to (II-c-6) has a wing group F at the remaining 8 - n connection points marked with * wearing,
in which

F

is H, optionally substituted C ₁ C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ -C ₂₂ - Iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, pseudohalogen, NO ₂ , a carboxyl, a sulfonic acid or sulfonate - or a hydroxy group.

M

für einen Steroidrest oder ein Derivat eines Steroidrestes stehen, insbesondere bevorzugt für einen Cholesterylrest oder ein Derivat des Cholesterylrestes der allgemeinen Formel (III-a) steht,

worin

R

für H, gegebenenfalls substituiertes C₁-C₂₂-Alkyl, C₁-C₂₂-Halogenalkyl, C₁-C₂₂-Alkenyl, C₁-C₂₂-Alkoxy, C₁-C₂₂-Thioalkyl, C₁-C₂₂-Iminoalkyl, C₁-C₂₂-Alkoxycarbonyl, C₁-C₂₂-Alkoxycarbonyloxy, einen Rest einer aliphatischen C₁-C₂₂-Alkancarbonsäure oder der Acrylsäure, Halogen, Pseudohalogen, NO₂ eine Carboxyl-, eine Sulfonsäure- bzw. Sulfonat- oder eine Hydroxygruppe steht.

Can also be preferred within the scope of the invention

M

stand for a steroid residue or a derivative of a steroid residue, particularly preferably stands for a cholesteryl residue or a derivative of the cholesteryl residue of the general formula (III-a),

wherein

R

for H, optionally substituted C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ -C ₂₂ Iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, pseudohalogen, NO ₂ a carboxyl, a sulfonic acid or sulfonate - or a hydroxy group.

The steroid residues or their derivatives are preferably linked via the C (3) atom of the A ring in the gonan backbone

worin R, R¹, R², R³ und R⁴ unabhängig voneinander die vorangehend für R genannte Bedeutung haben können. Allerdings handelt es sich hierbei lediglich um eine beispielhafte, nicht jedoch abschließende Aufzählung.In addition to the cholesteryl residue and its derivatives, steroid residues or derivatives of steroid residues can be, for example, those of the general formulas (III-b) to (III-e)

wherein R, R ¹ , R ² , R ³ and R ^{4 can} independently of one another have the meaning given for R. However, this is only an exemplary, but not exhaustive list.

In the general formulas (III-a) to (III-e) the configurations are on the individual stereo centers not shown. The present invention includes basically all known stereoisomers and mixtures thereof are preferred however, the naturally occurring stereoisomers and mixtures thereof.

The 3,4-alkylenedioxythiophenes according to the invention can be at least one chiral C atom contained in the alkylene radical A. In these cases, are within the scope of the invention under 3,4-alkylenedioxythiophenes according to the invention, both the pure stereoisomers, Enantiomers or diastereomers, as well as any mixtures to understand this.

Due to the presence of chiral compounds in liquid crystalline phases a helical superstructure can be formed. Such phases can be ferroelectric Have properties.

worin A, L und p oben genannte Bedeutung haben können,
nach bekannten Verfahren je nach Bedeutung von B und M durch Umsetzung mit entsprechenden Reaktanden hergestellt werden. Prinzipiell sind alle Verfahren unter Einsatz aller Reaktanden geeignet, die mit der Hydroxygruppe in Formel (V) die Knüpfung einer Ethergruppe (-0-) oder Oxycarbonylgruppe (-O-CO-) ermöglichen. Bei den bekannten Verfahren kann es sich je nach Bedeutung von B beispielsweise um Veresterungs- oder Veretherungsreaktionen handeln, jedoch kommen auch andere Reaktiontypen in Frage. Die Reaktanden können als gegenüber der Hydroxygruppe in Formel (V) reaktive funktionelle Gruppe beispielsweise eine Carbonsäuregruppe oder deren Derivat, eine Aldehydgruppe, Halogen oder andere enthalten. Beispielhaft seien hier Cholesterylchlorformiat, [(4'-Cyan-1,1'-biphenyl-4-yl)oxy]-carbonsäuren oder [(4'-Brom-1,1'-biphenyl-4-yl)oxy]carbonsäuren genannt. Geeignete Reaktanden, die nicht käuflich zu erwerben sind, können vor der Anknüpfung an die Verbindungen der Formel (V) aus Edukten enthaltend die Gruppierung B bzw. M oder aus Edukten, die durch ihre Verknüpfung erst die Gruppierungen B und M bilden, hergestellt werden. Es ist auch möglich B und M stufenweise anzuknüpfen, indem man die Hydroxyverbindungen der allgemeinen Formel (V) zunächst mit einem bifunktionellen Reaktanden umsetzt, der beispielsweise die Gruppierung B enthält, und das Zwischenprodukt nach Isolierung oder in situ mit einem weiteren beispielsweise die Gruppierung M enthaltenden Reaktanden zu den erfindungsgemäßen 3,4-Alkylendioxythiophenen umsetzt. Derartige Verfahren sind dem Fachmann ebenfalls bekannt. Als bifunktionelle Reaktanden seien beispielhaft α,ω-Dihalogenverbindungen, wie 1,6-Dibromhexan, genannt; als die Gruppierung M enthaltenden Reaktanden seien beispielhaft 4-(4-Alkoxyphenyl)phenol und 4-(4-Bromphenyl)phenol genannt.The 3,4-alkylenedioxythiophenes according to the invention can be obtained from hydroxy compounds of the general formula (V)

where A, L and p can have the meaning given above,
according to known methods depending on the importance of B and M by reaction with appropriate reactants. In principle, all processes using all reactants are suitable which, with the hydroxy group in formula (V), enable the formation of an ether group (-0-) or oxycarbonyl group (-O-CO-). Depending on the importance of B, the known processes can be, for example, esterification or etherification reactions, but other types of reaction are also possible. The reactants can contain, for example, a carboxylic acid group or its derivative, an aldehyde group, halogen or others as a functional group reactive towards the hydroxyl group in formula (V). Examples include cholesteryl chloroformate, [(4'-cyano-1,1'-biphenyl-4-yl) oxy] carboxylic acids or [(4'-bromo-1,1'-biphenyl-4-yl) oxy] carboxylic acids , Suitable reactants, which are not commercially available, can be prepared from starting materials containing the B or M group or from starting materials which only form the B and M groups through their linkage, before being linked to the compounds of the formula (V). It is also possible to link B and M in stages by first reacting the hydroxy compounds of the general formula (V) with a bifunctional reactant which contains, for example, the group B, and the intermediate product after isolation or in situ with another, for example containing the group M. Reactants to the 3,4-alkylenedioxythiophenes according to the invention. Such methods are also known to the person skilled in the art. Examples of bifunctional reactants are α, ω-dihalogen compounds, such as 1,6-dibromohexane; 4- (4-alkoxyphenyl) phenol and 4- (4-bromophenyl) phenol may be mentioned as examples of the reactants containing the group M.

The hydroxy compounds of the formula (V) can be prepared in an acid-catalyzed transetherification reaction from alkanetriols and 3,4-dialkoxythiophenes. Suitable 3,4-dialkoxythiophenes for this are in particular those with short-chain n-alkoxy groups, preferably methoxy, ethoxy and n-propoxy groups. This way of working is principally in Adv. Mater. 11 (1999), pp. 1379-1381. The preferred starting compounds EDT-methanol and hydroxy-PDT can also be prepared in a mixture in accordance with US Pat. No. 5,111,327. However, it is also possible to use the pure compounds which, for. B. are available by a chromatographic separation according to US-A 5,111,327. EDT-methanol can also be used directly in pure form according to Reynolds et al., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 38 (2), (1997), 320 using 2,3-dibromopropyl acetate.

The 3,4-alkylenedioxythiophenes according to the invention are outstandingly suitable for Manufacture of polythiophenes.

Therefore, the present invention also relates to the use of the invention 3,4-alkylenedioxythiophenes or mixtures thereof for the preparation of polythiophenes.

worin
A, L, p, M und B die oben genannte Bedeutung haben,
ausgenommen Polythiophene bestehend aus wiederkehrenden Einheiten der Formel (ii)

The invention furthermore relates to polythiophenes, characterized in that they contain recurring units of the general formula (IV)

wherein
A, L, p, M and B have the meaning given above,
excluding polythiophenes consisting of repeating units of the formula (ii)

In the context of the invention, these can be polythiophenes, the same or different contain recurring units of the general formula (IV), where in the case of different recurring units of the general formula (IV) the polythiophenes are copolymers. Depending on the arrangement of the different recurring units of the general formula (IV) can be are statistical, alternating, gradient or block copolymers.

worinPreferred polythiophenes according to the invention are characterized in that they contain repeating units of the general formula (IV-a) and / or (IV-b),

wherein

M and B have the meaning given above.

In these preferred polythiophenes according to the invention, the Invention the recurring units of the general formula (IV-a) and (IV-b) be contained in any molar ratio. Are particularly preferred polythiophenes according to the invention are the repeating units of the general Formula (IV-a) with a proportion of 65 to 99.9%, very particularly preferably with a share of 75 to 99.5% based on the total amount of the recurring Units, included, and the recurring units of general Formula (IV-b) particularly preferably with a proportion of 0.1 to 35%, very particularly preferably in a proportion of 0.1 to 25%, based on the total amount of substance recurring units included, with the proviso that the sum of both shares results in 100%.

In the context of the invention, all compounds are preferred under the term polythiophenes comprises at least 2 and at most 200, preferably at least 2 and contain at most 50, repeating units of the general formula (IV).

The polythiophenes according to the invention are preferably neutral and semiconducting or cationic and electrically conductive. In the event that it is cationic polythiophenes acts, the positive charges of the polythiophene polycations not shown in formulas (IV), (IV-a), (IV-b) because their exact number and their Position can not be determined correctly. The number of positive charges is however at least 1 and at most the total number of all recurring units in polythiophene.

To compensate for the positive charge contains the cationic form of the polythiophenes Anions, preferably polyanions, as counterions.

The anions of polymeric carboxylic acids preferably serve as polyanions, such as polyacrylic acids, polymethacrylic acid or polymaleic acids and polymers Sulphonic acids such as polystyrene sulphonic acids and polyvinyl sulphonic acids. This polycarbonate and sulfonic acids can also be copolymers of vinyl carbon and vinyl sulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene, his.

The anion of the polystyrene sulfonic acid is particularly preferred as the counter ion.

The molecular weight of the polyacids providing the polyanions is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000. The polyacids or their alkali salts are commercially available, e.g. Polystyrene sulfonic acids and Polyacrylic.

The polythiophenes containing recurring units of the general formula (IV) can by chemical or electrochemical oxidative polymerization of the 3,4-alkylenedioxythiophenes according to the invention can be prepared.

worin
A, L, p, M und B die oben genannte Bedeutung haben,
elektrochemisch oxidativ polymerisiert werden.The present invention thus furthermore relates to a process for the preparation of polythiophenes containing recurring units of the general formula (IV), with the exception of polythiophenes consisting of recurring units of the formula (ii), characterized in that compounds of the general formula (I)

wherein
A, L, p, M and B have the meaning given above,
are electrochemically oxidatively polymerized.

The electrochemical oxidative polymerization of the 3,4-alkylenedioxythiophenes according to the invention can be used at temperatures from -78 ° C to the boiling point of the Solvent or 3,4-alkylenedioxythiophene according to the invention made become. Preference is given to temperatures from -20 ° C to 60 ° C electrolyzed.

The reaction times are dependent on the monomer used, the one used Electrolytes, the selected electrolysis temperature and the applied one Current density from 1 minute to 24 hours.

If the 3,4-alkylenedioxythiophenes according to the invention under the electrolysis conditions are liquid, electropolymerization can be present or absent of solvents which are inert under the electrolysis conditions become; the electropolymerization of solid according to the invention under the electrolysis conditions 3,4-Alkylenedioxythiophenen is in the presence of among the Electrolysis conditions carried out inert solvents. In certain cases it may be advantageous to use solvent mixtures and / or the solvents Add solubilizers (detergents).

Examples of solvents which are inert under the electrolysis conditions are: Water; Alcohols such as methanol and ethanol; Ketones such as acetophenone; halogenated Hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and fluorocarbons; Esters such as ethyl acetate and butyl acetate; carbonate ester such as propylene carbonate; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane; Nitriles such as acetonitrile and benzonitrile; Sulfoxides such as dimethyl sulfoxide; sulfones such as dimethyl sulfone, phenylmethyl sulfone and sulfolane; liquid aliphatic Amides such as methylacetamide, dimethylacetamide, dimethylformamide, pyrrolidone, N-methylpyrrolidone, Caprolactam, N-methylcaprolactam; aliphatic and mixed aliphatic-aromatic ethers such as diethyl ether and anisole; liquid ureas like Tetramethyl urea or N-N-dimethyl-imidazolidinone. The polymerization can also take place out of lyotropic liquid crystalline phase.

The 3,4-alkylenedioxythiophenes according to the invention are used for electropolymerization or their solutions mixed with electrolyte additives. As electrolyte additives free acids or customary conductive salts are preferably used, which have a certain Have solubility in the solvents used. As electrolyte additives have e.g. proven: free acids such as p-toluenesulfonic acid, methanesulfonic acid, also salts with alkanesulfonate, aromatic sulfonate, tetrafluoroborate, hexafluorophosphate, Perchlorate, hexafluoroantimonate, hexafluoroarsenate and hexachloroantimonate anions and alkali, alkaline earth or optionally alkylated Ammonium, phosphonium, sulfonium and oxonium cations. Also against In the case of electrochemical polymerization, the above-mentioned polymeric counterions the electrolysis solution or the 3,4-alkylenedioxythiophenes according to the invention added as electrolyte additives or conductive salts.

The concentrations of the 3,4-alkylenedioxythiophenes according to the invention can between 0.01 and 100% by weight (100% by weight only with liquid thiophene); the concentrations are preferably 0.1 to 5% by weight.

The electropolymerization can be carried out batchwise or continuously become.

The current densities for electropolymerization can vary within wide limits; Current densities of 0.0001 to 100 mA / cm ² , preferably 0.01 to 40 mA / cm ² , are usually used. At these current densities, voltages of approximately 0.1 to 50 V are established.

worin
A, L, p, M und B die oben genannte Bedeutung haben,
chemisch oxidativ polymerisiert werden.The present invention also relates to a process for the preparation of polythiophenes containing recurring units of the general formula (IV), characterized in that compounds of the general formula (I)

wherein
A, L, p, M and B have the meaning given above,
can be chemically oxidatively polymerized.

The oxidative chemical polymerization of the 3,4-alkylenedioxythiophenes according to the invention depending on the oxidizing agent used and the desired reaction time generally at temperatures from -10 ° C to 250 ° C, preferably at Temperatures from 20 ° C to 200 ° C.

As a solvent for the 3,4-alkylenedioxythiophenes and / or Oxidizing agents are especially the following inert under the reaction conditions called organic solvents: aliphatic alcohols such as methanol, ethanol, i-propanol and butanol; aliphatic ketones such as acetone and methyl ethyl ketone; aliphatic carboxylic acid esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; Chlorinated hydrocarbons such as dichloromethane and dichloroethane; aliphatic nitriles such as acetonitrile, aliphatic sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; aliphatic carboxamide such as Methylacetamide and dimethylformamide; aliphatic and araliphatic ethers such as Diethyl ether and anisole. Water or mixtures of water can also be used used with the aforementioned organic solvents as a solvent become. The polymerization can also be carried out from a lyotropic liquid-crystalline phase respectively.

The oxidizing agents used are the oxidizing agents known to the person skilled in the art and suitable for the oxidative polymerization of thiophenes; these are for example in G. Koßmehl, Makromol. Chem., Macromol. Symp. 4, 45-64 (1986)). For practical reasons, inexpensive and easy-to-handle oxidizing agents, such as iron III salts of inorganic acids, such as, for example, FeCl ₃ , Fe (ClO ₄ ) ₃ or Fe ₂ (SO ₄ ) ₃ , and the iron III salts of organic acids and organic are preferred Residues of inorganic acids, also H ₂ O ₂ K ₂ Cr ₂ O ₇ , alkali and ammonium peroxodisulfates, alkali perborates, potassium permanganate, copper salts, such as copper tetrafluoroborate or cerium (IV) salts or CeO ₂ . The presence of catalytic amounts of metal ions, such as iron, cobalt, nickel, copper, molybdenum or vanadium ions, may be helpful.

For the oxidative polymerization of the 3,4-alkylenedioxythiophenes according to the invention and optionally subsequent oxidation of the poly-3,4-alkylenedioxythiophenes theoretically, about 2.25 equivalents of oxidizing agent are required per mole of thiophene (See, e.g., J. Polym. Sc. Part A Polymer Chemistry Vol. 26, p. 1287 (1988)). However, lower or higher equivalents of oxidizing agent can also be used be used. In the context of the invention, one is preferred per mole of thiophene Equivalents or more, particularly preferably 2 equivalents or more oxidizing agents used.

Examples of iron III salts of organic residues of inorganic acids are the iron III salts of the sulfuric acid semiesters of C ₁ -C ₂₀ alkanols, for example the Fe III salt of lauryl sulfate.

Examples of iron III salts of organic acids which may be mentioned are: the Fe III salts of C ₁ -C ₂₀ -alkanesulfonic acids, such as methane and dodecanesulfonic acid, aliphatic C ₁ -C ₂₀ -carboxylic acids such as 2-ethylhexylcarboxylic acid, aliphatic Perfluorocarboxylic acids such as trifluoroacetic acid and perfluorooctanoic acid, aliphatic dicarboxylic acids such as oxalic acid and especially aromatic sulfonic acids optionally substituted by C ₁ -C ₂₀ -alkyl groups such as benzenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid and cycloalkanesulfonic acids such as.

Mixtures of these aforementioned Fe III salts of organic acids can also be used become.

In addition, as counterions to the polythiophenes according to the invention, for the case that it is cationic polythiophenes, the possibly existing Anions of the oxidizing agent used, so that in the case of chemical oxidative polymerization does not add additional counterions is imperative.

worinIn preferred embodiments of the processes according to the invention, as compounds of the general formula (I) or mixtures thereof, compounds having a structure of the general formula (Ia) and / or (Ib),

wherein

B and M have the meaning given above.

In particularly preferred embodiments of the method according to the invention a mixture of 3,4-alkylenedioxythiophenes of the general formulas (I-a) and (I-b), wherein B and M have the meaning given above.

In the context of the invention, the 3,4-alkylenedioxythiophenes can be used in these mixtures of the general formulas (I-a) and (I-b) in any substance quantity ratio be included. The 3,4-alkylenedioxythiophenes of the general are preferred Formula (I-a) with a proportion of 65 to 99.9%, particularly preferably with a share of 75 to 99.5% based on the total amount of thiophenes, contain, and the 3,4-alkylenedioxythiophenes of the general formula (I-b) are preferred with a proportion of 0.1 to 35%, particularly preferably with a proportion from 0.1 to 25%, based on the total amount of thiophenes, with provided that the sum of both shares is 100%. The proportions of substance can the 3,4-alkylenedioxythiophenes of the general formulas (I-a) and (I-b) The proportions of the recurring units of the general Formulas (VI-a) and (VI-b) in the resulting polythiophenes according to the invention correspond, but can also be different from these.

In the context of the invention, C ₁ -C ₅ alkylene radicals can be methylene, ethylene, n-propylene, n-butylene or n-pentylene, and linear or cyclic C ₁ -C ₂₀ alkylene radicals can also be n-hexylene, n-heptylene, n- Octylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene or n-tetradecylene, n-hexadecylene, n-octadecylene or n-eicosylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene or cyclodecylene. Linear, branched or cyclic C ₁ -C ₂₂ -alkyl radicals can, for example, be methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl or n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl, n-docosyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, where cyclic alkyl radicals are at least C ₅ cycloalkyl radicals. C ₅ -C ₂₀ arylene residues can, for example, phenylene, naphthylene, biphenylene, fluorenylene, indenylene, cyclopentadienylene or anthracenylene and C ₆ -C ₂₀ aralkylene residues, for example o-, m-, p-tolylene, benzylene, 2,3-, 2, 4-, 2,5-, 2,6-, 3,4-, 3,5-xylylene or mesitylene. C ₂ -C ₂₀ heteroarylene radicals can be based on all heteroaromatic ring systems which, in addition to the C atoms, also have one to three heteroatoms selected from N, O or S in the heteroaromatic ring or ring system, such as, for example, pyrrole. Thiophene, furan, pyridine, indole, carbazole, pyrazole, imidazole or thiazole. In the context of the invention, C ₂ -C ₂₀₀ oligo- or polyether groups can contain those with one to 50 O atoms in the oligo or polyether chain, C ₂ -C ₈₀ oligo- or polyether groups can contain those with one to 20 O- Atoms, the smallest oligoether group with two carbon atoms is a dimethylene ether group (-CH ₂ -O-CH ₂ -). C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ -C ₂₂ iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ - C ₂₂ -alkoxycarbonyloxy and residues of aliphatic C ₁ -C ₂₂ -alkanecarboxylic acids can be derived from the above-mentioned C ₁ -C ₂₂ -alkyl radicals by appropriate substitution of an H atom by the functional group. Halogen can be, for example, fluorine, chlorine, bromine and iodine residues, pseudohalogen, for example cyan, thiocyan, isocyan or isothiocyanic residues. The preceding list serves to explain the invention by way of example and is not to be regarded as conclusive.

Halogen, pseudohalogen, keto, aldehyde, amino, hydroxyl, nitro, thiohydroxy, carboxyl, carboxylate, sulfonic acid or sulfonate groups, for example, are suitable as optional substituents, for example for C ₁ -C ₂₂ alkyl

Combining the mesogenic principle as in the case of the present invention Groups with polymers, so you can get liquid crystalline polymers. It However, due to the molecular order, they can also contain polymers improved properties such as higher conductivity, which arise Show liquid crystalline properties.

The polythiophenes according to the invention are suitable as components in electrical or electronic components, light-emitting components, in particular organic electrical or electronic components or light-emitting components, e.g. Luminous elements, photocells or organic transistors. Of they can also be used for antistatic coating, e.g. for finishing plastic films for the packaging of electronic components and for clean room packaging, for the antistatic finishing of cathode ray tubes or for antistatic Equipment for photographic films in optoelectronics, e.g. as transparent heating, as transparent electrodes, as printed circuit boards or for electrically colored window panes, or used in solar energy technology become.

The present invention therefore also relates to the use of the invention Polythiophenes as a component in electrical or electronic Components, light-emitting components, for antistatic coating, in optoelectronics or in solar energy technology.

The conductivity, for example, of components in electrical or electronic components, light-emitting components or antistatic coatings from the polythiophenes according to the invention can by a Temperature treatment (tempering) can be increased further. Under certain circumstances be passed through liquid crystalline phases. Annealing is preferred at temperatures from 80 ° C to 300 ° C, particularly preferably from 100 ° C to 250 ° C, for a period of 15 minutes to 6 hours, particularly preferably 30 Minutes to 4 hours. In the case of polythiophenes according to the invention, which according to chemical oxidative polymerization were produced, the tempering should be preferred after washing out excess reactants, such as Oxidizing agent or excess monomer, with a suitable solvent, preferably water or alcohols.

The polythiophenes according to the invention are preferably used in the form of conductive layers or coatings in electrical or electronic components, light-emitting components, for antistatic coating, in optoelectronics or in solar energy technology. These conductive layers are preferably produced by in situ polymerization of the corresponding 3,4-alkylenedioxythiophenes according to the invention and one or more oxidizing agents, optionally in the presence of additional counterions. The term in-situ polymerization is known to the person skilled in the art.

In preferred embodiments, the conductive layers increase subjected to the conductivity of a temperature treatment (tempering).

The conductive layers can be produced, for example, by the inventive 3,4-alkylenedioxythiophenes, oxidizing agents and optionally Counterions, together or in succession, optionally in the form of solutions, applied to the substrate to be coated and chemically oxidative to the inventive Polythiophenes are polymerized and any present Solvent is removed before, during or after the polymerization.

The solutions can be applied to the substrate to be coated according to known methods Methods, e.g. by impregnation, pouring, dripping, spraying, spraying on, Squeegee, brush or print.

Examples

The EDT-methanol / hydroxy-PDT mixture used below was according to US-A 5,111,327. Cholesteryl chloroformate is commercially available; [(4'-cyano-1,1'-biphenyl-4-yl) oxy] acetic acid, [(4'-cyano-1,1'-biphenyl-4-yl) oxy] butyric acid and [(4'-cyano-1,1'-biphenyl-4-yl) oxy] valeric acid and [(4'-bromo-1,1'-biphenyl-4-yl) oxy] valeric acid were according to J. Am. Chem. Soc. 119 (1997), Pp. 5825-5826.

Example 1:

2.46 g of a mixture of 80% EDT-methanol and 20% hydroxy-PDT (corresponding to 11.5 mmol EDT-methanol) are dissolved in dry methylene chloride and ice-cooled. 5.68 g (12.6 mmol) of cholesteryl chloroformate in dry methylene chloride are added to this cooled solution. Then 1.40 g (13.8 mmol) of triethylamine are slowly added dropwise and the ice bath is removed. The reaction mixture is stirred for 30 h at room temperature (23 ° C.), then another 2.64 g (5.9 mmol) cholesteryl chloroformate and 0.63 g (6.2 mmol) triethylamine in methylene chloride are slowly added. After a further 72 h reaction time, the solution is extracted three times with 1 M (molar) HCl and saturated NaHCO ₃ solution. The organic phase is dried with MgSO ₄ and the solvent is removed on a rotary evaporator at 20 mbar.

IR ν^-1 [cm^-1] = 2939, 2902, 2867, 2848; 1740
¹H-NMR (200 MHz, CDCl₃): δ [ppm] = 6,48 (s, 2% 2H, Nebenprodukt I-b1); 6,35, 6,32 (2*d, je 98 % 1H, ⁴ J _CH-CH: 3,91 Hz); 5,38 (d, 1H); 4,62 - 4,15 (m, 5H); 4,26 (dd, 1H, J _CH-CH: 4,05 Hz); 2,38 (d, 2H); 2,17 - 0,73 (m, 38H); 0,99 (s, 3H); 0,89 (d, 3H); 0,84 (d, 6H); 0,66 (s, 3H)
¹³C-NMR (50,3 MHz, CDCl₃): δ [ppm] = 154,16; 141,19, 140,93; 139,20; 123,14; 100,18, 99,98; 78,58; 71,26, 65,48, 65,18; 56,70; 56,16; 50,02; 42,34; 39,74; 39,53; 37,97; 36,85; 36,55; 36,21; 35,80; 31,92; 31,86; 28,23; 28,03; 27,66; 24,29; 23,85; 22,82; 22,59; 19,27, 18,74; 11,88
MS (FD, 5 kV): m/z = 585,5 [M+H]⁺ The crude product is purified by column chromatography twice (eluent: 1st CHCl ₃ , 2nd petroleum ether, eluted with CHCl ₃ ). The product is recrystallized from acetone, 0.93 g (I-a1) (in a mixture with 2% (I-b1); percentages, unless stated otherwise, based on the amount of substance) is obtained as a colorless powder.

IR ν ^-1 [cm ^-1 ] = 2939, 2902, 2867, 2848; 1740
¹ H NMR (200 MHz, CDCl ₃ ): δ [ppm] = 6.48 (s, 2% 2H, by-product I-b1); 6.35, 6.32 (2 * d, 98% each 1H, ⁴ J _CH-CH : 3.91 Hz); 5.38 (d. 1H); 4.62 - 4.15 (m, 5H); 4.26 (dd, 1H, J _CH-CH : 4.05 Hz); 2.38 (d. 2H); 2.17 - 0.73 (m, 38H); 0.99 (s, 3H); 0.89 (d, 3H); 0.84 (d, 6H); 0.66 (s, 3H)
¹³ C NMR (50.3 MHz, CDCl ₃ ): δ [ppm] = 154.16; 141.19, 140.93; 139.20; 123.14; 100.18, 99.98; 78.58; 71.26, 65.48, 65.18; 56.70; 56.16; 50.02; 42.34; 39.74; 39.53; 37.97; 36.85; 36.55; 36.21; 35.80; 31.92; 31.86; 28.23; 28.03; 27.66; 24.29; 23.85; 22.82; 22.59; 19.27, 18.74; 11.88
MS (FD, 5 kV): m / z = 585.5 [M + H] ⁺

Phase transitions (determined with a polarizing microscope):

Mp 131.9 ° C, clear point 137.5 ° C (on 1st heating)

K 131.9 FC 137.5 I (K = crystalline, FC = liquid crystalline, I = isotropic liquid; the Numerical values between the phase names indicate the transition temperature in ° C, e.g. K 131.9 FC = transition from the crystalline to the liquid-crystalline phase at 131.9 ° C)

Example 2:

IR ν^-1 [cm^-1] = 2992, 2979, 2942, 2909, 2226, 1751 und 1743 , 1604, 1582 und 1495
¹H-NMR (500 MHz, DMSO-d₆): δ (ppm) = 7,87 (d, 2H, ³ J _CH-CH: 8,51 Hz,); 7,81 (d, 2H ³ J _CH-CH: 8,51 Hz); 7,68 (d, 2H, ³ J _CH-CH: 8,83 Hz); 7,06 (d, 2H, ³ J _CH-CH: 8,83 Hz); 6,61 (d, 1H, ⁴ J _CH-CH: 3,78 Hz,); 6,58 (d, 1H, ⁴ J _CH-CH: 3,78 Hz); 4,93 (s, 2H); 4,53 - 4,32 (m, 3H); 4,26 (dd, 1H, J _CH-CH: 11,67 Hz); 3,96 (dd, 1H, J _CH-CH: 11,67 Hz).
¹³C-NMR (125,75 MHz, DMSO-d₆): δ (ppm) = 166,69; 156,38; 142,32; 139,28, 139,17, 130,99; 129,45; 126,53; 125,20; 117,19; 113,45; 107,52; 98,24, 98,20; 69,49; 63,03, 62,74; 60,70. MS (EI, 70 eV): m/z = 407 M⁺ 100 % 208 C₁₄H₁₀NO⁺ 24,3 % 178 C₁₃H₈N⁺ 49,1 % 155 C₇H₇O₂S+ 22,5 % 1.73 g of a mixture of 80% EDT-methanol and 20% hydroxy-PDT (corresponding to 8.08 mmol EDT-methanol), 1.64 g of N, N'-dicyclohexylcarbodiimide and 0.13 g of 4- (dimethylamino) pyridine are dissolved in 100 ml CH ₂ Cl ₂ and cooled to approx. 0 ° C in an ice bath. 2.00 g [(4'-cyano-1,1'-biphenyl-4-yl) oxy] acetic acid are added in portions over the course of 1 h with stirring and ice cooling. The reaction is then continued at 23 ° C. for 42.5 h. The N, N'-dlcyclohexylurea formed is then filtered off. The filtrate is extracted twice in succession with 200 ml of 1 M HCl, 200 ml of saturated NaHCO ₃ solution and 200 ml of saturated NaCl solution. The organic phase is dried over MgSO ₄ and, after filtering off the magnesium sulfate on a rotary evaporator, freed from the solvent. 3.71 g of crude product are obtained, which is purified by column chromatography with n-hexane / ethyl acetate 3: 2. 0.39 g of the pure ester of EDT-methanol (I-a2) are obtained as colorless crystals.

IR ν ^-1 [cm ^-1 ] = 2992, 2979, 2942, 2909, 2226, 1751 and 1743, 1604, 1582 and 1495
¹ H NMR (500 MHz, DMSO-d ₆ ): δ (ppm) = 7.87 (d, 2H, ³ J _CH-CH : 8.51 Hz,); 7.81 (d, 2H ³ J _CH-CH: 8.51 Hz); 7.68 (d, 2H, ³ J _CH-CH : 8.83 Hz); 7.06 (d, 2H, ³ J _CH-CH : 8.83 Hz); 6.61 (d, 1H, ⁴ J _CH-CH : 3.78 Hz,); 6.58 (d, 1H, ⁴ J _CH-CH : 3.78 Hz); 4.93 (s, 2H); 4.53 - 4.32 (m, 3H); 4.26 (dd, 1H, J _CH-CH : 11.67 Hz); 3.96 (dd, 1H, J _CH-CH : 11.67 Hz).
¹³ C NMR (125.75 MHz, DMSO-d ₆ ): δ (ppm) = 166.69; 156.38; 142.32; 139.28, 139.17, 130.99; 129.45; 126.53; 125.20; 117.19; 113.45; 107.52; 98.24, 98.20; 69.49; 63.03, 62.74; 60.70. MS (EI, 70 eV): m / z = 407 M ⁺ 100% 208 C ₁₄ H ₁₀ NO ⁺ 24.3% 178 C ₁₃ H ₈ N ⁺ 49.1% 155 C ₇ H ₇ O ₂ S + 22.5%

Melting range: 125.2 - 127.7 ° C (observed on the polarizing microscope). Example 3:

1.06 g of a mixture of 80% EDT-methanol and 20% hydroxy-PDT (corresponding to 6.19 mmol; 4.95 mmol based on the main component EDT-methanol), 1.04 g (5.04 mmol) N. N'-dicyclohexylcarbodiimide and 0.15 g (1.22 mmol) of 4- (dimethylamino) pyridine are dissolved in 50 ml of CH ₂ Cl ₂ and cooled in an ice bath. 1.42 g (5.05 mmol) of [(4'-cyan-1,1'-biphenyl-4-yl) oxy] butyric acid (see formula) are added in portions to the ice-cooled solution with stirring. After 1 h the reaction is continued at room temperature. After a further 64 h, the colorless precipitate formed (N, N'-dicyclohexylurea) is filtered off. The clear, colorless solution is shaken out successively with 75 ml of 1N HCl, 75 ml of saturated NaHCO ₃ solution and 75 ml of saturated NaCl solution. The clear organic phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. 2.38 g of crude product are obtained.

The purification is carried out by column chromatographic separation. Mobile solvent: n-hexane / ethyl acetate 3: 2. '
Yield (I-a3) / (I-b3): 1.25 g colorless powder (56.8% of theory) 2 isomers: approx. 95% (I-a3) and 5% (I-b3)

Data for (I-a3) / (I-b3), molar ratio 95: 5

IR ν ^-1 [cm ^-1 ] = 3117; 2969, 2947, 2923, 2905, 2884; 2222; 1734 1597, 1582, 1486; 827.815
¹ H NMR (500 MHz, DMSO-d ₆ ): δ [ppm] = 7.86 (d, 2H); 7.81 (d. 2H); 7.68 (d, 2H, ³ J _CH-CH : 8.83 Hz); 7.03 (d, 2H, ³ J _CH-CH : 8.83 Hz); 6.79 (s, 5% 2H, (I-b3)); 6.58 (s, 95% 2H); 4.47 - 4.38 (m, 1H); 4.36 - 4.23 (m, 3H); 4.15 (d, 5% 4H, (I-b3)); 4.05 (t, 2H); 4.00 (dd, 1H); 2.55 (t, 2H); 2.02 (tt, 2H)
¹³ C NMR (125.75 MHz, DMSO-d ₆ ): δ [ppm] = 172.46; 159.23; 144.36; 141.20, 141.11; 132.90; 130.58; 128.44; 126.97; 119.13; 115.23; 109.25; 100.08; 71.46; 66.72; 65.10; 62.24; 30.08; 24.22 MS (EI, 70 eV): m / z = 435 M ⁺ 39.8% 264 C ₁₇ H ₁₄ NO ₂ ⁺ 12.6% 241 C ₁₁ H ₁₃ O ₄ S ⁺ 44.5% 195 C ₁₃ H ₈ NO ⁺ 34.3% 155 C ₇ H ₇ O ₂ S ⁺ 100%

Phase transitions (determined with a polarizing microscope):

Melting range: 119.8 - 121.9 ° C (on 1st heating) isotropic at 118.8 ° C on 2. Heating

K 116.9 FC 117.0 I (with 3rd heating)

Example 4:

2.20 g of a mixture of 80% EDT-methanol and 20% hydroxy-PDT (corresponding to 12.9 mmol; 10.3 mmol based on the main component EDT-methanol), 2.10 g (10.2 mmol) N. N'-dicyclohexylcarbodiimide and 1 spatula tip 4- (dimethylamino) pyridine are dissolved in 80 ml CH ₂ Cl ₂ and cooled in an ice bath. 3.00 g (10.2 mmol) of [(4'-cyan-1,1'-biphenyl-4-yl) oxy] valeric acid (see formula) are added to the cold (0 ° C.) solution with spatulas while stirring. Residues of [(4'-cyan-1,1'-biphenyl-4-yl) oxy] valeric acid are dissolved in 20 ml of CH ₂ Cl ₂ and added to the reaction. After 1 h the reaction is continued at room temperature. After a further 48 h, the colorless precipitate formed (N, N'-dicyclohexylurea) is filtered off. The clear, colorless solution is shaken out successively with three times 75 ml of 1N HCl, 75 ml of saturated NaHCO ₃ solution and 75 ml of saturated NaCl solution. The organic phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. 4.70 g of crude product are obtained.

The purification is carried out by column chromatographic separation. Solvent: n-hexane / Ethyl acetate 3: 2.

Yield pure product (2 isomers: approx. 97% (I-a4) and 3% (I-b4)):
1.40 g colorless powder (30.7% of theory)

Data for (I-a4) / (I-b4), molar ratio 97: 3:

IR ν ^-1 [cm ^-1 ] = 3122, 3109; 2962, 2938, 2918, 2879, 2864; 2220; 1733; 1600, 1579, 1481; 826th
¹ H NMR (500 MHz, DMSO-d ₆ ): δ [ppm] = 7.85 (d, 2H, ³ J _CH-CH : 8.52 Hz); 7.81 (d, 2H, ³ J _CH-CH : 8.52 Hz); 7.67 (d, 2H, ³ J _CH-CH : 8.83 Hz); 7.03 (d, 2H, ³ J _CH-CH : 8.83 Hz); 6.79 (s, 3% 2H, (I-b4)); 6.59 (s, 97% 2H); 4.44 - 4.36 (m, 1H); 4.33 - 4.20; 4.09 - 3.94 (2 * m, 2 * 3H); 4.14 (d, 3% 4H, (I-b4)); 2.43 (t, 2H); 1.83 - 1.62 (m, 4H)
¹³ C NMR (125.75 MHz, DMSO-d ₆ ): δ [ppm] = 172.92; 159.62; 144.62; 141.46; 133.12; 130.67; 128.65; 127.17; 119.37; 115.44; 109.45; 100.30; 71.70; 67.56; 65.33; 62.32; 33.24; 28.25; 21.44

Phase transitions (determined with a polarizing microscope):

K 103.0 FC 105.8 1 (at 1st heating, start at 95 ° C, heating rate <1 ° C / min) MS (EI, 70 eV): m / z = 449 M ⁺ 25.1% 255 C ₁₂ H ₁₅ O ₄ S ⁺ 68.9% 195 C ₁₃ H ₉ NO ⁺ 31.2% 155 C ₇ H ₇ O ₂ S ⁺ 100%

Example 5:

3.26 g of a mixture of 80% EDT-methanol and 20% hydroxy-PDT (corresponding to 18.9 mmol; 15.1 mmol based on the main component EDT-methanol), 3.14 g (15.2 mmol) N, N'-dicyclohexylcarbodiimide and 0.3 g (2.45 mmol) of 4- (dimethylamino) pyridine are dissolved in 100 ml of CH ₂ Cl ₂ and cooled in an ice bath. 5.25 g (15.0 mmol) of [(4'-bromo-1,1'-biphenyl-4-yl) oxy] -valeric acid are added to the ice-cooled solution with stirring in a spatula. After 1 h the reaction is continued at room temperature. After a further 65 h, the colorless precipitate (N, N'-dicyclohexylurea) formed is filtered off. The clear, colorless solution is shaken out successively with 250 ml of 1N HCl, 150 ml of saturated NaHCO ₃ solution and 150 ml and 100 ml of saturated NaCl solution once. The organic phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. 7.98 g of crude product are obtained.

The purification is carried out by column chromatographic separation. Solvent: n-hexane / Ethyl acetate 4: 1.

Yield (I-a5) (contains about 5% isomer (I-b5)):
3.06 g colorless powder (6.08 mmol = 40.5% of theory)

Data for (I-a5):

IR ν ^-1 [cm ^-1 ] = 3108; 2956, 2933, 2905, 2868, 1740; 1606, 1579, 1488; 815
¹ H NMR (500 MHz, DMSO-d ₆ ): δ [ppm] = 7.65-7.50 (m, 6H); 6.99 (d. 2H); 6.79 (s, 5% 2H), 6.59 (s, 95% 2H); 4.44 - 4.36 (m, 1H); 4.33 - 4.19; 4.17 - 4.12 (m, 5% 4H); 4.07 - 3.94 (2 * m, 2 * 3H); 2.43 (t, 2H); 1.81 - 1.63 (m, 4H)
¹³ C NMR (125.75 MHz, DMSO-d ₆ ): δ [ppm] = 172.92; 158.88; 141.46; 141.35; 139.37; 132.04; 131.43; 128.57; 128.05; 120.34; 115.32; 100.30; 71.70; 67.49; 65.33; 62.32; 33.25; 28.29; 21.46

Phase transitions:

Liquid crystalline phases were observed on the polarizing microscope.

DSC:

1.Heating : onset: 98.50 ° C, maximum: 100.68 ° C, final set: 103.63 ° C,

Heating rate: 5 ° C / min, keep at 130 ° C for 5 min

1. Cool down:

1.Peak: onset: 82.41 ° C, minimum: 82.39 ° C, endset: 81.58 ° C,

2nd peak: onset: 81.01 ° C, minimum: 81.00 ° C, final set: 80.75 ° C,
Heating rate: - 1 ° C / min

2. Heating:

1.Peak: onset: 82.43 ° C, maximum: 84.00 ° C, final set: 85.35 ° C,

2nd peak: onset: 92.75 ° C, minimum: 94.57 ° C, final set: 96.00 ° C,
Heating rate: 2 ° C / min MS (EI, 70 eV): m / z = 502 M ⁺ 37.4% 255 C ₁₂ H ₁₅ O ₄ S ⁺ 86.0% 248 C ₁₂ H ₁₀ BrO ⁺ 22.1% 155 C ₇ H ₇ O ₂ S ⁺ 100.0%

Example 6: Neutral polythiophene made from (I-a5) and (I-b5)

0.3 g (0.6 mmol) of the thiophene mixture prepared according to Example 5 (I-a5 / I-b5, molar ratio 95: 5) are dissolved in 12 ml of chloroform. 0.15 g (1.5 mmol) of finely powdered calcium carbonate is slurried in this solution. 0.24 g (1.48 mmol) of ferric chloride (anhydrous) are added to this mixture at 23 ° C. with stirring at intervals of 1 h in two equal portions. The mixture is stirred at 23 ° C. for a further 4 h. Then with 12 ml of methylene chloride. After adding 6 ml of aqueous ammonia (26%), the mixture is heated under reflux for 2 h. The solid is then filtered off. The solid is washed with chloroform and the combined organic phases are refluxed again with 6 ml of aqueous 26% ammonia with vigorous stirring for 1 h. The organic phase is washed with 0.05 molar EDTA solution (Na ethylenediaminetetraacetate) and then with water, dried over sodium sulfate and concentrated. The solid residue is boiled in methanol for 30 min and filtered hot. 0.13 g (43.3% of theory) of polythiophene with repeating units (IV-a5) and (IV-b5) are obtained.

Characterization by MALDI-TOF-MS (Fig. 1). Example 7: Neutral polythiophene made from (I-a5) and (I-b5)

0.6 g (1.19 mmol) of the thiophene prepared according to Example 5 (I-a5 / I-b5, molar ratio 95: 5) are dissolved in 24 ml chloroform. In this solution 0.475 g (4.75 mmol) of finely powdered calcium carbonate is slurried. To this mixture are at 23 ° C with stirring at intervals of 1 h in three same portions 0.77 g (4.75 mmol) of ferric chloride (anhydrous) added. The The mixture is stirred at 23 ° C. for a further 4 h. Then with 24 ml of methylene chloride. After adding 12 ml of aqueous ammonia (26%), the mixture is heated under reflux for 2 h. The solid is then filtered off. The solid is treated with chloroform washed and the combined organic phases again with 12 ml of aqueous 26% ammonia heated to reflux with vigorous stirring for 1 h. The organic phase is mixed with 0.05 molar EDTA solution (Na ethylenediaminetetraacetate) and then washed with water, dried over sodium sulfate and concentrated. The solid residue is boiled in methanol for 30 min and filtered hot. 0.2 g (33.3% of theory) of polythiophene with repeating units (IV-a5) and (IV-b5) are obtained.

Characterization by gel permeation chromatography (in THF, polystyrene standard, RI detection): M _n = 2300; M _w = 9900 Example 8: Cationic, highly conductive polythiophene from (I-a5) and (I-b5) as a coating by in situ polymerization

0.22 g of the thiophene prepared according to Example 5 (I-a5 / I-b5, molar ratio 95: 5) are dissolved in 6.625 g of boiling n-butanol. To the hot solution 1.562 g of a 40% solution of ferric tosylate in n-butanol are rapidly (Baytron® CB 40; manufacturer: H.C. Starck GmbH) and the mixture a glass plate preheated to approx. 100 ° C (wet film layer thickness 24 µm). After drying for 10 min at 100 ° C and cooling to room temperature (23 ° C) the coating is washed with deionized water and blow dried. The surface resistance (two-point method) is measured at 461 Ω / square. The plate was annealed again at 150 ° for 30 min when Surface resistance after cooling to 23 ° C was measured at 211 Ω / square.

Example 9: Cationic polythiophene (tetrachloroferrate) from (I-a5) and (I-b5) as powder

Under N ₂ protective gas, 1.0 g (1.99 mmol) of the thiophene prepared according to Example 5 (I-a5 / I-b5, molar ratio 95: 5) are dissolved in 7.7 ml of acetonitrile and heated to reflux. 1.875 g (11.56 mmol) of ferric chloride (anhydrous) in 19 ml of acetonitrile are added dropwise to this solution over 30 minutes under reflux. The solution is refluxed for a further 16 h. The insoluble precipitate of cationic polythiophene is then filtered off with suction and washed several times with acetonitrile. Yield 0.89 g of cationic polythiophene with tetrachloroferrate as counter anion.

Example 10: a) Reaction of an EDT-methanol / hydroxy-PDT mixture with 1,6-dibromohexane (Reactant containing group B):

The process is carried out under an Ar protective gas atmosphere. 3.03 g sodium hydride (60% in Mineral oil, 75.8 mmol) are washed twice with dry toluene and then suspended in 100 ml of toluene. The suspension is heated to 80 ° C and 10 g EDT-methanol / hydroxy-PDT (80:20, 58.1 mmol (based on the mixture)) dissolved slowly added dropwise in 80 ml of toluene within 40 min. The colorless suspension turns yellowish brown. After a further hour, 70.9 g (290.5 mmol) 1,6-dibromohexane added. The solution is stirred at 80 ° C for 100 min, then the heating is switched off and stirred at room temperature (23 ° C.) for a further 20 h. 15 ml of acetone are added and after half an hour are still 8 ml of water added. The colorless precipitate dissolves and arises 2 phases. The reaction mixture is twice with 90 ml of 1 molar (M) HCl shaken out. The toluene phase is extracted again with 180 ml of 1 M HCl.

The collected HCl phases are extracted three times with 90 ml of chloroform. The collected chloroform phases are discarded and the HCl phase extracted three times with 50 ml of toluene. The HCl phase is then discarded. The collected toluene phases are shaken out three times with 120 ml of saturated aqueous NaCl solution each. The toluene phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. The brown liquid thus obtained is purified by column chromatography (ethyl acetate: hexane first 1:19 later 1: 4).

Yield: 12.95 g (38.6 mmol (based on the mixture) = 66.5% of theory) yellowish crystals, content of PDT derivative: 16%.

b) reaction of the product mixture from a) with 4- (4-bromophenyl) phenol (Reactant containing group M)

Ausbeute:

1.Fraktion: 1,57 g (3,12 mmol = 68,7 % der Theorie) farblose Kristalle (I-a6) im Gemisch mit 14 % (I-b6).
2.Fraktion: 0,33 g (0,66 mmol = 14,4 % der Theorie) farblose, blättchenartige Kristalle (I-a6) im Gemisch mit 15 Mol-% (I-b6).

1.13 g (4.54 mmol) of 4- (4-bromophenyl) phenol, 1.69 g (5.04 mmol) of the product mixture from a) (16% PDT derivative, 84% EDT derivative and 1.81 g (5.56 mmol) of Cs ₂ CO ₃ are suspended in 30 ml of DMF and stirred at room temperature for 70 h, 90 ml of buffer pH 7 (Aldrich) are added to the suspension and the solution is extracted twice with 100 ml of diethyl ether collected ether phases are dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. The crude product is recrystallized from methanol / methylene chloride. The colorless crystals obtained are filtered off, washed with methanol and dried in vacuo over P ₂ O ₅ .

Yield:

1st fraction: 1.57 g (3.12 mmol = 68.7% of theory) of colorless crystals (I-a6) mixed with 14% (I-b6).
2nd fraction: 0.33 g (0.66 mmol = 14.4% of theory) colorless, flake-like crystals (I-a6) in a mixture with 15 mol% (I-b6).

IR ν ^-1 [cm ^-1 ] = 2934, 2868, 2859, 1604, 1580, 1491, 806.
¹ H NMR (500 MHz, CDCl ₃ ): δ [ppm] = 7.52 (d, 2H, ³ J _CH-CH : 8.51 Hz); 7.47 (d, 2H, ³ J _CH-CH : 8.83 Hz); 7.41 (d, 2H, ³ J _CH-CH : 8.51 Hz); 6.95 (d, 2H, ³ J _CH-CH : 8.83 Hz); 6.46 (s, 14% 2H); 6.33, 6.32 (2 * d, 86% 1H each); 4.34-4.27 (m, 86% 1H); 4.27-4.20 (m, 86% 1H); 4.10 (dd, 14% 4H); 4.05 (dd, 86% 1H); 3.99 (t, 2H); 3.87-3.80 (m, 14% 1H); 3.69 (dd, 86% 1H, J _CH-CH : 10.40 Hz); 3.60 (dd, 86% 1H, J _CH-CH : 10.40 Hz); 3.56 (t, 14% 1H); 3.51 (t, 86% 2H); 1.81 (m, 2H); 1.63 (m, 2H); 1.54-1.39 (2 * m, 2H each)
¹³ C NMR (125.75 MHz, DMSO-d ⁶ ): δ [ppm] = 158.97; 149.42; 141.73, 141.67; 139.37; 132.03; 131.34; 128.54, 128.04; 120.32; 115.30; 105.92; 100.04, 99.97; 77.34, 71.61, 68.91; 72.82, 71.16, 68.87, 67.82, 65.85; 29.71; 29.35, 28.98; 25.69.

Phase transitions (determined with a polarizing microscope):

K 86.2 FC 87.7 1 (with 1st heating)

K 86.2 FC 88.1 I (with 2nd heating)

MS (E1, 70 eV): m / z = 502 M ⁺ 96.6% 248 C ₁₂ H ₉ BrO ⁺ 63.5% 172 C ₇ H ₈ O ₃ S ⁺ 19.8% 83 C ₄ H ₃ S ⁺ 64.6%

Example 11: a) Preparation of a reactant containing the group M

Ausbeute:

2,07 g (8,08 mmol = 46,7 % der Theorie) cremefarbene Kristalle.

3.22 g (17.3 mmol) of 4,4'-dihydroxybiphenyl, 2.62 g (17.3 mmol) of 1-bromopentane and 2.53 g (18.3 mmol) of K ₂ CO ₃ are dissolved in 150 ml of acetone suspended and boiled under reflux for 26 h, then the mixture is stirred for a further 24 h at room temperature. The precipitate is filtered off, discarded and the acetone is completely removed from the filtrate on a rotary evaporator. The yellowish precipitate formed is purified by column chromatography (4 hexanes: 1 ethyl acetate).

Yield:

2.07 g (8.08 mmol = 46.7% of theory) cream-colored crystals.

b) reaction of the product mixture from Example 10a) with the reactant Example 11a)

Ausbeute:

0,87 g (1,7 mmol = 87,4 % der Theorie (bezogen auf das Gemisch)) (I-a7) im Gemisch mit 15,5% (I-b7)

0.50 g (1.95 mmol) of the reactant from Example 11a), 0.75 g (2.24 mmol) of the product mixture from Example 10a) (16% PDT derivative, 84% EDT derivative) and 0.76 g (2.33 mmol) of Cs ₂ CO ₃ are suspended in 15 ml of DMF and stirred for 5 days at room temperature. 50 ml of saturated aqueous NaHCO ₃ solution are added to the suspension and it is extracted twice with 50 ml of chloroform each time. The collected chloroform phases are shaken out again with 50 ml of saturated aqueous NaHCO ₃ solution; the chloroform phase is then extracted twice with 50 ml of saturated aqueous NaCl solution. The chloroform phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. The crude product is recrystallized from methanol / methylene chloride. The beige crystals obtained are filtered off, washed with methanol and dried in vacuo over P ₂ O ₅ .

Yield:

0.87 g (1.7 mmol = 87.4% of theory (based on the mixture)) (I-a7) in a mixture with 15.5% (I-b7)

IR ν ^-1 [cm ^-1 ] = 3040, 3067, 2957, 2936, 2861, 1606, 1568, 1491, 807.
¹ H NMR (500 MHz, CDCl ₃ ): δ [ppm] = 7.51-7.41 (m, 4H); 6.99-6.89 (m, 4H); 6.46 (s, 15.5% 2H); 6.33, 6.32 (2 * d, 84.5% 2H); 4.33-4.27 (m, 84.5% 1H); 4.26-4.20 (m, 84.5% 1H); 4.09 (dd, 15.5% 4H); 4.05 (dd, 84.5% 1H); 3.98 (t, 4H, 13-H); 3.86-3.80 (m, 15.5% 1H); 3.68 (dd, 84.5% 2H, J _CH-CH : 10.40 Hz); 3.59 (dd, 84.5% 2H, J _CH-CH : 10.40 Hz); 3.55 (t, 15.5% 1H); 3.51 (t, 84.5% 2H); 1.86-1.74 (m, 4H); 1.63 (m, 2H); 1.55-1.33 (m, 8H); 0.94 (t, 3H).
¹³ C-NMR (125.75 MHz, CDCl ₃ : δ [ppm] = 157.20, 157.12; 148.11; 140.57, 140.53; 132.35 132.25; 126.62; 113 , 69; 104.25; 98.65, 98.53; 76.83, 70.64; 71.62, 70.87, 68.10, 67.03, 66.85, 65.19; 28.80 ; 28.45, 28.22, 27.98, 27.20; 24.87, 24.81; 21.46; 13.03.

Phase transitions (determined with a polarizing microscope):

K 101.1 FC 103.1 I (on 1st heating, start 92 ° C, <1 ° C / min) MS (EI, 70 eV): m / z = 510 M ⁺ 100.0% 256 C ₁₇ H ₂₀ O ₂ ⁺ 10.8% 186 C ₁₂ H ₁₀ O ₂ ⁺ 51.9% 83 C ₄ H ₃ S ⁺ 15.3%

Example 12: a) Reaction of an EDT-methanol-hydroxy-PDT mixture with 1,5-dibromopentane (Reactant containing group B):

It is operated under nitrogen. 8 g of sodium hydride (60% in mineral oil, 0.2 mol) are washed twice with dry toluene and then suspended in 200 ml of toluene. The suspension is heated to 80 ° C. and 20 g of EDT-methanol / hydroxy-PDT (80:20, 116.2 mmol, based on the mixture) dissolved in 160 ml of toluene are added dropwise over the course of 1.5 h. The colorless suspension turns brown. After a further hour, 134 g (581 mmol) of 1,5-dibromopentane are added. The solution is stirred at 80 ° C. for 2 hours, then the heating is switched off and the mixture is stirred at room temperature for a further 12 hours. 16 ml of water is carefully added to stop the reaction. The reaction mixture is shaken out twice with 180 ml of 1N HCl each. The toluene phase is shaken out again with 360 ml of 1N HCl. The collected HCl phases are extracted three times with 180 ml of chloroform. The collected chloroform phases are discarded and the HCl phase extracted three times with 100 ml of toluene. The HCl phase is then discarded. The collected toluene phases are extracted three times with 240 ml of saturated aqueous NaCl solution. The toluene phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. The excess 1,5-dibromopentane is distilled off at 60 ° C. in a high vacuum. The crude product is purified by column chromatography (ethyl acetate: hexane 1: 4).
Yield : 19.49 g (60.7 mmol = 52.1% of theory) greenish oil, content of PDT derivative: 7%

b) reaction of the product mixture from a) with 4- (4-bromophenyl) phenol (Reactant containing group M)

1.43 g (5.74 mmol) of 4- (4-bromophenyl) phenol, 1.93 g (6.01 mmol) of the product mixture from a) (7% PDT derivative, 93% EDT derivative) and 2, 56 g (7.86 mmol) Cs ₂ CO ₃ are suspended in 50 ml DMF and stirred for 4 d at room temperature. Working up is carried out analogously to Example 10 b).

Ausbeute:

1. Fraktion: 1,87 g (3,82 mmol = 66,6 % der Theorie) (I-a8) im Gemisch mit 5 % (I-b8)
2. Fraktion: 0,57 g (1,17 mmol = 20,3 % der Theorie) (I-a8) im Gemisch mit 9 % (I-b8)
3. Fraktion 0,17 g (0,35 mmol = 6,1 % der Theorie) (I-a8) im Gemisch mit 31 % (I-b8).

The crude product is recrystallized from methanol / methylene chloride. The colorless precipitate is filtered off, washed with methanol and dried in vacuo.

Yield :

1st fraction: 1.87 g (3.82 mmol = 66.6% of theory) (I-a8) in a mixture with 5% (I-b8)
2nd fraction: 0.57 g (1.17 mmol = 20.3% of theory) (I-a8) in a mixture with 9% (I-b8)
3rd fraction 0.17 g (0.35 mmol = 6.1% of theory) (I-a8) mixed with 31% (I-b8).

IR ν ^-1 [cm ^-1 ] = 2942, 2912, 2870 1604, 1579, 1482 816.
¹ H-NMR (500 MHz, CDCl ₃ ): δ [ppm] = 7.52, 7.40 (2 * d, 2H each); 7.46 (d. 2H); 6.95 (d, 2-H); 6.46 (s, 5% 2H); 6.33, 6.32 (2 * d, 95% 1H each); 4.36 - 4.27 (m, 95% 1H); 4.24 (dd, 95% 1H, J _CH-CH : 11.67 Hz, superimposed on dd); 4.10 (dd, 5% 2H); 4.06 (dd, 95% 1H, J _CH-CH : 11.67 Hz); 3.99 (t, 2H); 3.88 - 3.80 (m, 5% 1H); 3.69 (dd, 95% 1H, J _CH-CH : 10.40 Hz); 3.60 (dd, 95% 1H, J _CH-CH : 10.40 Hz); 3.53 (t, 95% 2H); 1.83, 1.67 (2 * m, 2H each); 1.62 - 1.47 (m, 2H)
¹³ C NMR (125.75 MHz, CDCl ₃ ): δ [ppm] = 159.28; 141.98, 141.94; 140.16; 132.73; 132.17; 128.67, 128.35; 121.13; 115.27; 100.10, 99.98; 73.04, 72.20; 69.58, 68.25, 66.61; 29.69, 29.44; 23.08

K 109,1°C FC ca. 120°C I (1. Heizen)

K 107,7°C FC ca. 126°C I (2. Heizen)

Elementaranalyse: berechnet 58,90 % C 5,15 % H gefunden 59,11 % C 5,11 % H MS (EI, 70 eV): m/z = 488 M⁺ 38,9 % 241 C₁₂H₁₇O₃S⁺ 54,7 % 155 C₇H₇O₂S⁺ 38,6 % Phase transitions (determined with a polarizing microscope):

K 109.1 ° C FC approx. 120 ° CI (1st heating)

K 107.7 ° C FC approx. 126 ° CI (2nd heating)

Elemental analysis: calculated 58.90% C 5.15% H found 59.11% C 5.11% H MS (EI, 70 eV): m / z = 488 M ⁺ 38.9% 241 C ₁₂ H ₁₇ O ₃ S ⁺ 54.7% 155 C ₇ H ₇ O ₂ S ⁺ 38.6%

Example 13: Cationic, highly conductive polythiophene from (I-a8) and (I-b8) as a coating by in situ polymerization

0.21 g of the thiophene (I-a8) / (I-b8) prepared according to Example 12 (molar ratio 95: 5) are dissolved hot in 6.625 g of n-butanol. To the hot solution 1.562 g of a 40% solution of ferric tosylate in n-butanol are rapidly (Baytron® CB 40; manufacturer: H.C. Starck GmbH) and the mixture a glass plate preheated to approx. 80 ° C (wet film layer thickness 24 µm). After drying for 10 min at 80 ° C and cooling to room temperature (23 ° C) the coating is washed with deionized water and blow dried. 601 Ω / square are measured as the surface resistance (two-point method). The plate is annealed again at 150 ° for 30 min as surface resistance after cooling to 23 ° C, 190 Ω / square are measured.

Example 14: a) Reaction of an EDT-methanol / hydroxy-PDT mixture with 1,6-dibromohexane (Reactant containing group B):

The reaction is carried out in accordance with Example 10 a).

b) reaction of the product mixture from a) with 4- (4-propylphenyl) benzoic acid (Reactant containing group M)

1.00 g (4.16 mmol) 4- (4-propylphenyl) benzoic acid, 1.57 g (4.68 mmol) of the product mixture from a) (16% PDT derivative, 84% EDT derivative) and 1, 67 g (5.13 mmol) of Cs ₂ CO ₃ are suspended in 46 ml of DMF and stirred for 5 d at room temperature. 50 ml of saturated aqueous NaHCO ₃ solution are added to the suspension, and the solution is extracted twice with 50 ml of chloroform each time. For better phase separation, 50 ml of water is added. The collected organic phases are washed with 75 ml aq. NaHCO ₃ solution, shaken again and then shaken twice with 50 ml of saturated aqueous NaCl solution. The chloroform phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator and in an oil pump vacuum.

Ausbeute:

2,00 g (4,04 mmol = 97 % d. Theorie) (I-a9) im Gemisch mit 15 % (I-b9)

IR ν^-1 [cm^-1] = 2931, 2866; 1711; 1607, 1580, 1485; 835
¹H-NMR (500 MHz, CDCl₃): δ [ppm] = 8,09 (d, 2H); 7,65 (d, 2H); 7,54, 7,28 (2*d, je 2H); 6,46 (s, 15 % 2H); 6,33, 6,31 (2*d, je 85 % 1H, ⁴ J _CH-CH: 3,47 Hz); 4,34 (t, 2H); 4,32 - 4,26 (m, teilweise überlagert 85 % 1H); 4,23 (dd, 85 % 1H überlagert dd); 4,09 (dd, überlagert; 15 % 2H); 4,05 (dd, 85 % 1H); 3,87 - 3,80 (m, 15 % 1H); 3,68 (dd, 85 % 1H, J _CH-CH: 10,40 Hz); 3,59 (dd, 85 % 1H, J _CH-CH: 10,40 Hz); 3,55 (t, 85 % 1H); 3,51 (t, 85 % 2H); 2,64 (t, 2H); 1,85 - 1,74 (m, 2H); 1,74 * 1,56 (m, 4H); 1,54 - 1,37 (m, 4H); 0,97 (t, 3H)
¹³C-NMR (125,75 MHz, CDCl₃): δ [ppm] = 166,60; 145,53, 142,60, 137,34; 141,57, 141,54; 130,02, 129,06, 127,08, 126,79; 128,87; 99,67, 99,55; 77,88; 72,53, 71,87; 71,65, 69,82; 69,14, 66,21, 64,91; 37,70; 29,80; 29,44, 28,72; 25,90, 25,76; 24,52; 13,86The beige crude product is purified by column chromatography (eluent hexane / ethyl acetate 4: 1). A clear liquid is obtained which crystallizes to a colorless precipitate in the freezer.

Yield :

2.00 g (4.04 mmol = 97% of theory) (I-a9) in a mixture with 15% (I-b9)

IR ν ^-1 [cm ^-1 ] = 2931, 2866; 1711; 1607, 1580, 1485; 835
¹ H NMR (500 MHz, CDCl ₃ ): δ [ppm] = 8.09 (d, 2H); 7.65 (d. 2H); 7.54, 7.28 (2 * d, 2H each); 6.46 (s, 15% 2H); 6.33, 6.31 (2 * d, 85% each 1H, ⁴ J _CH-CH : 3.47 Hz); 4.34 (t, 2H); 4.32 - 4.26 (m, partially overlaid 85% 1H); 4.23 (dd, 85% 1H superimposed on dd); 4.09 (dd, overlaid; 15% 2H); 4.05 (dd, 85% 1H); 3.87 - 3.80 (m, 15% 1H); 3.68 (dd, 85% 1H, J _CH-CH : 10.40 Hz); 3.59 (dd, 85% 1H, J _CH-CH : 10.40 Hz); 3.55 (t, 85% 1H); 3.51 (t, 85% 2H); 2.64 (t, 2H); 1.85 - 1.74 (m, 2H); 1.74 * 1.56 (m, 4H); 1.54 - 1.37 (m, 4H); 0.97 (t, 3H)
¹³ C NMR (125.75 MHz, CDCl ₃ ): δ [ppm] = 166.60; 145.53, 142.60, 137.34; 141.57, 141.54; 130.02, 129.06, 127.08, 126.79; 128.87; 99.67, 99.55; 77.88; 72.53, 71.87; 71.65, 69.82; 69.14, 66.21, 64.91; 37.70; 29.80; 29.44, 28.72; 25.90, 25.76; 24.52; 13.86

K 49,1 °C FC 56,4°C I (1. Heizen, < 1°C/min)

K 53,1 °C FC 58,1 °C I (2. Heizen, < 1°C/min)

Phase transitions (determined with a polarizing microscope):

K 49.1 ° C FC 56.4 ° CI (1st heating, <1 ° C / min)

K 53.1 ° C FC 58.1 ° CI (2nd heating, <1 ° C / min)

1. Heizen: onset: 50,58°C, Maximum: 53,19°C, Endset: 57,38°C,

2. Heizen: onset: 46,88°C, Maximum: 49,35°C, Endset: 52,77°C,

3. Heizen: onset: 45,25°C, Maximum: 49,44°C, Endset: 52,82°C,
Heizrate stets 1°C/min

Elementaranalyse: berechnet 70,42 % C 6,93 % H gefunden 70,49 % C 6,91 % H MS (EI, 70 eV): m/z = 494 M⁺ 7,6 % 255 C₁₃H₁₀O₃S⁺ 11,2 % 223 C₁₆H₁₅O⁺ 24,3 % 83 C₄H₃S⁺ 32,4 % Phase transitions (determined with DSC):

1.Heating : onset: 50.58 ° C, maximum: 53.19 ° C, final set: 57.38 ° C,

2.Heating : onset: 46.88 ° C, maximum: 49.35 ° C, final set: 52.77 ° C,

3.Heating : onset: 45.25 ° C, maximum: 49.44 ° C, final set: 52.82 ° C,
Heating rate always 1 ° C / min

Elemental analysis: calculated 70.42% C 6.93% H found 70.49% C 6.91% H MS (EI, 70 eV): m / z = 494 M ⁺ 7.6% 255 C ₁₃ H ₁₀ O ₃ S ⁺ 11.2% 223 C ₁₆ H ₁₅ O ⁺ 24.3% 83 C ₄ H ₃ S ⁺ 32.4%

Example 15 : Cationic, highly conductive polythiophene from (I-a9) and (I-b9) as a coating by in situ polymerization

0.215 g of the thiophene (I-a9) / (I-b9) prepared according to Example 14 (molar ratio 85:15) are dissolved warm in 6.625 g of n-butanol. Become the solution quickly 1.562 g of a 40% solution of ferric tosylate in n-butanol (Baytron® CB 40; manufacturer: H.C. Starck GmbH) and the mixture on a doctor blade preheated to approx. 80 ° C (wet film thickness 24 µm). After drying for 10 min at 80 ° C and cooling to room temperature (23 ° C) the coating is washed with deionized water and blow dried. As Surface resistance (two-point method) is measured at 473 Ω / square. The Plate is annealed again at 150 ° C for 30 min, as surface resistance after Cooling to 23 ° C, 110 Ω / square are measured.

Example 16: a) Reaction of an EDT-methanol / hydroxy-PDT mixture with 1,4-dibromobutane (Reactant containing group B):

Ausbeute:

8,15 g (26,5 mmol = 45,7 % d. Theorie) grünlich-braune Flüssigkeit mit einem Gehalt an PDT-Derivat von 12 %

IRν^-1 [cm^-1] = 3110 2938, 2918, 2868;, 1482, 1452, 1427, 1374, 1247, 1184, 1123, 1019,856,758
¹H-NMR (500 MHz, CDCl₃): δ [ppm] = 6,47 (s, 12% 2H); 6,34, 6,33 (2*d, je 88% 1H, ⁴ J _CH-CH: 3,78 Hz); 4,37 - 4,27 (m, 93 % 1H); 4,23 (dd, 88% 1H, J _CH-CH: 11,66 Hz, mit Überlagerung); 4,10 (dd, 12% 4H); 4,05 (dd, 1H, J _CH-CH: 11,66 Hz); 3,88 - 3,80 (m, 12% 1H); 3,69 (dd, 88% 1H, J _CH-CH: 10,40 Hz); 3,60 (dd, 88% 1H, J _CH-CH: 10,40 Hz); 3,59 (t, 7 % 1H); 3,54 (t, 88% 2H); 3,44 (t, 2H); 2,07 - 1,64 (2*m, je 2H)
¹³C-NMR (125,75 MHz, CDCl₃): δ [ppm] = 149,46; 141,92, 141,86; 105,74; 100,11, 99,03; 78,34; 71,92, 69,15; 72,99, 71,30, 69,58, 66,52; 34,00; 29,89, 28,51; 28,88 Elementaranalyse: berechnet 43,01 % C 4,92 % H gefunden 43,11 % C 4,88 % H MS (EI, 70 eV): m/z = 306 M⁺ 27,6 % 227 C₁₁H₁₅O₃S⁺ 25,4 % 156 C₇H₇O₂S⁺ 21,3 % 135 C₄H₈Br⁺ 40,2 % It is operated under nitrogen. 4 g of sodium hydride (60% in mineral oil, 0.1 mol) are washed twice with dry toluene, then suspended in 100 ml of toluene. This suspension is heated to 80 ° C. and 10 g of EDT-methanol / hydroxy-PDT (approx. 80:20, 58.1 mmol, based on the mixture) dissolved in 80 ml of toluene are added dropwise over the course of 35 minutes. The colorless suspension turns brown. After a further hour, 45 ml (82.35 g = 0.381 mol) of 1,4-dibromobutane are added. The solution is stirred at 80 ° C. for 5 h, then the heating is switched off and the mixture is stirred at room temperature for a further 12 h. 8 ml of water is carefully added to stop the reaction. The reaction mixture is shaken out twice with 90 ml of 1N HCl each. The toluene phase is shaken out again with 180 ml of 1N HCl. The collected HCl phases are extracted three times with 90 ml of chloroform. The collected chloroform phases are discarded and the HCl phase extracted three times with 50 ml of toluene. The HCl phase is then discarded. The collected toluene phases are shaken out three times with 120 ml of saturated aqueous NaCl solution each. The toluene phase is dried over MgSO ₄ , the drying agent is filtered off and the solvent is removed on a rotary evaporator. The excess 1,4-dibromobutane is distilled off at 60 ° C. in an oil pump vacuum. The crude product is purified by column chromatography (mobile phase: ethyl acetate / hexane 1: 4).

Yield:

8.15 g (26.5 mmol = 45.7% of theory) greenish-brown liquid with a PDT derivative content of 12%

IR ν ^-1 [cm ^-1 ] = 3110 2938, 2918, 2868 ;, 1482, 1452, 1427, 1374, 1247, 1184, 1123, 1019.856.758
¹ H NMR (500 MHz, CDCl ₃ ): δ [ppm] = 6.47 (s, 12% 2H); 6.34, 6.33 (2 * d, 88% each 1H, ⁴ J _CH-CH : 3.78 Hz); 4.37 - 4.27 (m, 93% 1H); 4.23 (dd, 88% 1H, J _CH-CH : 11.66 Hz, with overlay); 4.10 (dd, 12% 4H); 4.05 (dd, 1H, J _CH-CH : 11.66 Hz); 3.88 - 3.80 (m, 12% 1H); 3.69 (dd, 88% 1H, J _CH-CH : 10.40 Hz); 3.60 (dd, 88% 1H, J _CH-CH : 10.40 Hz); 3.59 (t, 7% 1H); 3.54 (t, 88% 2H); 3.44 (t, 2H); 2.07 - 1.64 (2 * m, 2H each)
¹³ C NMR (125.75 MHz, CDCl ₃ ): δ [ppm] = 149.46; 141.92, 141.86; 105.74; 100.11, 99.03; 78.34; 71.92, 69.15; 72.99, 71.30, 69.58, 66.52; 34.00; 29.89, 28.51; 28,88 Elemental analysis: calculated 43.01% C 4.92% H found 43.11% C 4.88% H MS (EI, 70 eV): m / z = 306 M ⁺ 27.6% 227 C ₁₁ H ₁₅ O ₃ S ⁺ 25.4% 156 C ₇ H ₇ O ₂ S ⁺ 21.3% 135 C ₄ H ₈ Br ⁺ 40.2%

b) reaction of the product mixture from a) with 4-hydroxybenzoic acid methyl ester (Reactant containing group M)

Ausbeute:

1,15 g (3,04 mmol = 85,6 % d. Theorie) (I-a10 mit einem Gehalt an PDT-Derivat von 16 %

IR ν^-1 [cm^-1] = 3111, 2948, 2872; 1711; 1604, 1578, 1483
¹H-NMR (500 MHz, CDCl₃): δ [ppm] = 7,97 (d, 2H, 14-H); 6,89 (d, 2H, 13-H); 6,47 (s, 16 % 2H, A-H); 6,32 (s, 84 % 2H, 1-H, 2-H); 4,39 - 4,26 (m, 84 % 1H, 6-H); 4,23 (dd, 84 % 1H, 5a-H überlagert dd von Ca-H); 4,12 (dd, 16 % 2H, Cb-H); 4,05 (dd, 84 % 1H, 5b-H überlagert von 11-H); 4,03 (t, 2H, 11-H überlagert von 5b-H); 3,88 (s, 3H, 17-H); 3,70 (dd, 84 % 1H, 7a-H); 3,62 (dd, 84 % 1H, 7b-H); 3,57 (t, 84 % 2H, 8-H); 1,98 - 1,84,1,84 - 1,69 (2*m, je 2H, 9-H, 10-H)
¹³C-NMR (125,75 MHz, CDCl₃): δ [ppm] = 165,84; 161,73; 140,51, 140,48; 130,55; 141,41; 113,00; 98,68, 98,59; 71,60, 70,52; 68,16, 66,71, 65,11; 50,82; 25,11, 24,870.54 g (3.55 mmol) of methyl 4-hydroxybenzoate, 1.23 g (4.00 mmol) of the product mixture from a) (88% EDT derivative, 12% PDT derivative) and 3.39 g (10, 4 mmol) of Cs ₂ CO ₃ are suspended in 30 ml of DMF and stirred for 4 d at room temperature. Working up is carried out analogously to Example 14 b). The crude product is purified by column chromatography (mobile phase hexane / ethyl acetate 4: 1). A yellowish, viscous oil is obtained.

Yield:

1.15 g (3.04 mmol = 85.6% of theory) (I-a10 with a content of PDT derivative of 16%

IR ν ^-1 [cm ^-1 ] = 3111, 2948, 2872; 1711; 1604, 1578, 1483
¹ H NMR (500 MHz, CDCl ₃ ): δ [ppm] = 7.97 (d, 2H, 14-H); 6.89 (d, 2H, 13-H); 6.47 (s, 16% 2H, A -H); 6.32 (s, 84% 2H, 1-H, 2-H); 4.39 - 4.26 (m, 84% 1H, 6-H); 4.23 (dd, 84% 1H, 5a-H overlaid dd of Ca- H); 4.12 (dd, 16% 2H, Cb -H); 4.05 (dd, 84% 1H, 5b-H superimposed on 11-H); 4.03 (t, 2H, 11-H superimposed on 5b-H); 3.88 (s, 3H, 17-H); 3.70 (dd, 84% 1H, 7a-H); 3.62 (dd, 84% 1H, 7b-H); 3.57 (t, 84% 2H, 8-H); 1.98 - 1.84.1.84 - 1.69 (2 * m, each 2H, 9-H, 10-H)
¹³ C NMR (125.75 MHz, CDCl ₃ ): δ [ppm] = 165.84; 161.73; 140.51, 140.48; 130.55; 141.41; 113.00; 98.68, 98.59; 71.60, 70.52; 68.16, 66.71, 65.11; 50.82; 25.11, 24.87

K 40,8°C FC 48,7°C I (1. Heizen, < 1°C/min)

Phase transitions (determined with a polarizing microscope):

K 40.8 ° C FC 48.7 ° CI (1st heating, <1 ° C / min)

1. Heizen: onset: 39,57°C, Maximum: 44,88°C, Endset: 50,06°C

Elementaranalyse: berechnet 60,00 % C 5,86 % H gefunden 60,20 % C 6,01 % H MS (EI, 70 eV): m/z = 378 M⁺ 16,5 % 227 C₁₁H₁₅O₃S⁺ 26,0 % 155 C₇H₇O₂S⁺ 32,1 % Phase transitions (determined with DSC):

1.Heating : onset: 39.57 ° C, maximum: 44.88 ° C, final set: 50.06 ° C

Elemental analysis: calculated 60.00% C 5.86% H found 60.20% C 6.01% H MS (EI, 70 eV): m / z = 378 M ⁺ 16.5% 227 C ₁₁ H ₁₅ O ₃ S ⁺ 26.0% 155 C ₇ H ₇ O ₂ S ⁺ 32.1%

Example 17: Cationic, highly conductive polythiophene from (I-a10) and (I-b10) as a coating by in situ polymerization

0.165 g of the thiophene (I-a10) / (I-b10) prepared according to Example 16 (molar ratio 84: 16) are dissolved warm in 6.625 g of n-butanol. To the Solution quickly become 1.562 g of a 40% solution of ferric tosylate in n-butanol (Baytron® CB 40; manufacturer: H.C. Starck GmbH) and the mixture on a glass plate preheated to approx. 80 ° C (wet film layer thickness 24 µm). After drying for 10 min at 100 ° C and cooling to room temperature (23 ° C) the coating is washed with deionized water and blow dried. The surface resistance (two-point method) is measured at 276 Ω / square. The plate is annealed again at 150 ° C for 30 min as surface resistance after cooling to 23 ° C, 66 Ω / square are measured.

Example 18: a) Reaction of an EDT-methanol-hydroxy-PDT mixture with 1,5-dibromopentane (Reactant containing group B):

The implementation corresponds to Example 12 a).

b) reaction of the product mixture from a) with 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester (Reactant containing group M)

1.08 g (4.46 mmol) of ethyl 4'-hydroxybiphenyl-4-carboxylate, 1.50 g (4.67 mmol) of the product mixture from a) (7% PDT derivative, 93% EDT derivative) and 1, 55 g (4.76 mmol) of Cs ₂ CO ₃ are suspended in 40 ml of DMF and stirred for 4 d at room temperature. Working up is carried out analogously to Example 12 b).

Ausbeute:

Fraktion 1: 1,08 g (2,24 mmol = 50,2 % d. Theorie) (I-a11) im Gemisch mit 3 % PDT-Derivat (I-b11)
Fraktion 2: 0,77 g (1,60 mmol = 35,8 % d. Theorie) (I-a11) im Gemisch mit 6 % PDT-Derivat (I-b11)
Fraktion 3: 0,18 g (0,37 mmol = 8,4 % d. Theorie) (I-a11) im Gemisch mit 30 % PDT-Derivat (I-b11)

IR ν^-1 [cm^-1] = 2946, 1899, 2869; 1703; 1600, 1581, 1489; 826
¹H-NMR (500 MHz, CDCl₃): δ [ppm] = 8,08 (d, 2H); 7,61 (d, 2H); 7,56 (d, 2H); 6,97 (d, 2H); 6,47 (s, 3 % 2H); 6,33, 6,32 (2*d, je 97 % 1H); 4,39 (q, 2H), 4,35 - 4,27 (m, 97 % 1H); 4,24 (dd, 1H,J _CH-CH: 11,66 Hz überlagert dd); 4,11 (dd, 3 % 2H); 4,06 (dd, 1H, J _CH-CH: 11,66 Hz); 4,01 (t, 2H); 3,69 (dd, 1H, J _CH-CH: 10,40 Hz); 3,61 (dd, 1H, J _CH-CH: 10,40 Hz); 3,54 (t, 2H); 1,87 - 1,79, 1,73 - 1,63, 1,59 - 1,51 (3*m, je 2H); 1,41 (t, 3H)
¹³C-NMR (125,75 MHz, CDCl₃): δ [ppm] = 167,00; 159,68; 145,52; 141,97, 141,93; 132,70; 130,44, 128,73, 126,79; 128,94; 115,29; 100,09, 99,98; 73,04, 72,19; 69,58, 68,25, 66,61; 61,29; 29,68, 29,42; 23,08; 14,78The crude product is recrystallized from methanol / methylene chloride. The colorless precipitate is filtered off, washed with methanol and dried in vacuo.

Yield:

Fraction 1: 1.08 g (2.24 mmol = 50.2% of theory) (I-a11) in a mixture with 3% PDT derivative (I-b11)
Fraction 2: 0.77 g (1.60 mmol = 35.8% of theory) (I-a11) in a mixture with 6% PDT derivative (I-b11)
Fraction 3: 0.18 g (0.37 mmol = 8.4% of theory) (I-a11) in a mixture with 30% PDT derivative (I-b11)

IR ν ^-1 [cm ^-1 ] = 2946, 1899, 2869; 1703; 1600, 1581, 1489; 826
¹ H NMR (500 MHz, CDCl ₃ ): δ [ppm] = 8.08 (d, 2H); 7.61 (d. 2H); 7.56 (d. 2H); 6.97 (d. 2H); 6.47 (s, 3% 2H); 6.33, 6.32 (2 * d, 97% 1H each); 4.39 (q, 2H), 4.35 - 4.27 (m, 97% 1H); 4.24 (dd, 1H, J _CH-CH : 11.66 Hz superimposed on dd); 4.11 (dd, 3% 2H); 4.06 (dd, 1H, J _CH-CH : 11.66 Hz); 4.01 (t, 2H); 3.69 (dd, 1H, J _CH-CH : 10.40 Hz); 3.61 (dd, 1H, J _CH-CH : 10.40 Hz); 3.54 (t, 2H); 1.87-1.79, 1.73-1.63, 1.59-1.51 (3 * m, 2H each); 1.41 (t, 3H)
¹³ C NMR (125.75 MHz, CDCl ₃ ): δ [ppm] = 167.00; 159.68; 145.52; 141.97, 141.93; 132.70; 130.44, 128.73, 126.79; 128.94; 115.29; 100.09, 99.98; 73.04, 72.19; 69.58, 68.25, 66.61; 61.29; 29.68, 29.42; 23.08; 14.78

K 87,7°C FC 91,6°C I (1. Heizen, < 1°C/min)

K 87,8°C FC 94,0°C I (2. Heizen, < 1°C/min) bei 70,8°C bereits FC, jedoch nach
Tempern rekristallisiert

Phase transitions (determined with a polarizing microscope):

K 87.7 ° C FC 91.6 ° CI (1st heating, <1 ° C / min)

K 87.8 ° C FC 94.0 ° CI (2nd heating, <1 ° C / min) at 70.8 ° C already FC, but after
Annealing recrystallized

1. Heizen: onset: 84,45°C, Maximum: 86,63°C, Endset: 90,08°C,
Heizrate: 10°C/min

Elementaranalyse: berechnet 67,20 % C 6,27 % H gefunden 67,28 % C 6,23 % H MS (EI, 70 eV): m/z = 482 M⁺ 68,5 % 241 C₁₂H₁₇O₃S⁺ 67,5 % 155 C₇H₇O₂S⁺ 40,6 % Phase transitions (determined with DSC)

1. Preheat: Onset: 84.45 ° C, maximum: 86.63 ° C, endset: 90.08 ° C,
Heating rate: 10 ° C / min

Elemental analysis: calculated 67.20% C 6.27% H found 67.28% C 6.23% H MS (EI, 70 eV): m / z = 482 M ⁺ 68.5% 241 C ₁₂ H ₁₇ O ₃ S ⁺ 67.5% 155 C ₇ H ₇ O ₂ S ⁺ 40.6%

Example 19: Cationic, highly conductive polythiophene from (I-a11) and (I-b11) as a coating by in situ polymerization

0.2111 g of the thiophene (I-a11) / (I-b11) prepared according to Example 18 (fraction 1, Substance ratio 97: 3) are dissolved in 6.625 g of n-butanol. To the solution 1.562 g of a 40% solution of ferric tosylate in n-butanol are rapidly (Baytron® CB 40; manufacturer: H.C. Starck GmbH) and the mixture a glass plate preheated to approx. 80 ° C (wet film layer thickness 24 µm). After drying for 10 min at 80 ° C and cooling to room temperature (23 ° C) the coating is washed with deionized water and blow dried. 170 Ω / square are measured as the surface resistance (two-point method). The plate was annealed again at 150 ° for 30 min as surface resistance after cooling to 23 ° C, 58 Ω / square are measured.

Claims (18)

3,4-alkylenedioxythiophenes, characterized in that they are optionally substituted by a link B with a mesogenic group,
except the 3,4-alkylenedioxythiophene of the formula (i)

3,4-alkylenedioxythiophenes according to Claim 1, characterized in that they are compounds of the general formula (I),

wherein

A

represents a C ₁ -C ₅ alkylene radical which is substituted at any point by a linker L and optionally carries further substituents,

L

represents a methylene group,

p

represents 0 or an integer from 1 to 6,

M

represents an n-functional mesogenic group,

n

represents an integer from 1 to 8 and

B

represents a link of the general formula (B)

wherein

q

represents 0 or 1,

r, s

stand for 0 or 1, with the proviso that if r stands for 1 s stands for 0 and vice versa or both can stand for 0,

t

represents 0 or 1,

sp

for a spacer selected from optionally substituted linear or cyclic C ₁ -C ₂₀ alkylene, C ₅ -C ₂₀ arylene, C ₂ -C ₂₀ heteroarylene, with additionally one to three heteroatoms selected from N, O or S can be present in the heteroaromatic ring or ring system, C ₆ -C ₂₀ aralkylene, C ₂ -C ₂₀₀ oligo- or polyether groups,

m

represents 0 or 1,

Q

represents O, S or NH.

3,4-alkylenedioxythiophenes according to claim 1 or 2, characterized in that

M

represents an n-functional group of the general formulas (II-a) or (II-b),

wherein

X ¹ , X ² , X ³

independently selected for optionally substituted structures

Z ¹ , Z ²

independently selected for structures from

stands,
in which

R ^x and R ^y

independently of one another for H, optionally substituted C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ - C ₂₂ iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, pseudohalogen, NO _{2 is} a carboxyl or a hydroxy group,

H

represents an integer from 1 to 10,

w

is an integer from 1 to 5,

x, y, z

independently represent 0 or 1, and

n

represents 1 or 2, where

in the event that n stands for 1, the group of the general formulas (II-a) or (II-b) bears a wing group F at one of the linking points marked with *,
in which

F

for H, optionally substituted C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ -C ₂₂ Iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, pseudohalogen, a nitro (NO ₂ -), a carboxyl , a sulfonic acid or sulfonate or a hydroxy group.

3,4-alkylenedioxythiophenes according to claim 1 or 2, characterized in that

M

represents an n-functional group selected from the general formulas (II-c-1) to (II-c-6),

wherein

n

represents an integer from 1 to 8, where

in the event that n stands for an integer less than 8, the group selected from the general formulas (II-c-1) to (II-c-6) has a wing group F at the remaining 8-n connection points marked with * wearing,
in which

F

for H, optionally substituted C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ -C ₂₂ Iminoalkyl, C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, pseudohalogen, a nitro (NO ₂ -), a carboxyl , a sulfonic acid or sulfonate or a hydroxy group.

3,4-alkylenedioxythiophenes according to claim 1 or 2, characterized in that

M

stands for a steroid residue or a derivative of a steroid residue.

3,4-alkylenedioxythiophenes according to claim 5, characterized in that

M

represents a cholesteryl radical or a derivative of the cholesteryl radical of the general formula (III-a),

wherein

R

for H, optionally substituted Ci-C22-alkyl, C ₁ -C ₂₂ haloalkyl, C ₁ -C ₂₂ alkenyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ thioalkyl, C ₁ -C ₂₂ iminoalkyl , C ₁ -C ₂₂ alkoxycarbonyl, C ₁ -C ₂₂ alkoxycarbonyloxy, a residue of an aliphatic C ₁ -C ₂₂ alkane carboxylic acid or acrylic acid, halogen, pseudohalogen, a nitro (NO ₂ -), a carboxyl, a Sulfonic acid or sulfonate or a hydroxy group.

3,4-alkylenedioxythiophenes or mixtures of 3,4-alkylenedioxythiophenes according to at least one of Claims 1 to 6, characterized in that they have a structure of the general formula (Ia) and / or (Ib),

wherein
B and M have the meaning given in at least one of claims 2 to 6. Use of the 3,4-alkylenedioxythiophenes or mixtures of 3,4-alkylenedioxythiophenes according to at least one of claims 1 to 7 Manufacture of polythiophenes. Polythiophenes, characterized in that they contain repeating units of the general formula (IV),

wherein
A, L, p, M and B have the meaning given in at least one of claims 2 to 6,
excluding polythiophenes consisting of repeating units of the formula (ii)

Polythiophenes according to Claim 9, characterized in that they contain repeating units of the general formula (IV-a) and / or (IV-b),

wherein
M and B have the meaning given in at least one of claims 2 to 6. Polythiophenes according to claim 9 or 10, characterized in that they are cationic and electrically conductive and contain anions bound as counterions to compensate for the positive charge. Polythiophenes according to claim 11, characterized in that the counterions are polyanions of polymeric carboxylic acids or polymeric sulfonic acids. Polythiophenes according to claim 9 or 10, characterized in that they are neutral and semiconducting. Process for the preparation of polythiophenes according to at least one of Claims 9 to 13, characterized in that compounds of the general formula (I),

wherein
A, L, p, M and B have the meaning given in at least one of claims 2 to 6,
are electrochemically oxidatively polymerized. Process for the preparation of polythiophenes, characterized in that compounds of the general formula (I),

wherein

A

represents a C ₁ -C ₅ alkylene radical which is substituted at any point by a linker L and optionally carries further substituents,

L

represents a methylene group,

p

represents 0 or an integer from 1 to 6,

n

represents an integer from 1 to 8 and

B

represents a link of the general formula (B)

wherein

q

represents 0 or 1,

r, s

stand for 0 or 1, with the proviso that if r stands for 1 s stands for 0 and vice versa or both can stand for 0,

t

represents 0 or 1,

sp

for a spacer selected from optionally substituted linear or cyclic C ₁ -C ₂₀ alkylene, C ₅ -C ₂₀ arylene, C ₂ -C ₂₀ heteroarylene, with additionally one to three heteroatoms selected from N, O or S can be present in the heteroaromatic ring or ring system, C ₆ -C ₂₀ aralkylene, C ₂ -C ₂₀₀ oligo- or polyether groups,

m

represents 0 or 1,

Q

represents O, S or NH, and

M

has the meaning given in at least one of claims 2 to 6,

can be chemically oxidatively polymerized. Polythiophenes characterized in that they contain repeating units of the general formula (IV),

wherein
A, L, p and B have the meaning given in claim 15 and

M

has the meaning given in at least one of claims 2 to 6,

obtainable by a method according to claim 15. Use of the polythiophenes according to at least one of Claims 9 to 13 and 16 as a component in electrical or electronic components, light-emitting Components, for antistatic coating, in optoelectronics or in solar energy technology. Use of the polythiophenes according to at least one of Claims 9 to 13 and 16 for the production of conductive layers.

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